Light Treatment of Chromium Catalysts and Related Catalyst Preparation Systems and Polymerization Processes

ABSTRACT

Catalyst preparation systems and methods for preparing reduced chromium catalysts are disclosed, and can comprise irradiating a supported chromium catalyst containing hexavalent chromium with a light beam having a wavelength within the UV-visible light spectrum. Such reduced chromium catalysts have improved catalytic activity compared to chromium catalysts reduced by other means. The use of the reduced chromium catalyst in polymerization reactor systems and olefin polymerization processes also is disclosed, resulting in polymers with a higher melt index.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/732,020, filed on Sep. 17, 2018, the disclosure ofwhich is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to chromium catalysts, methodsfor preparing the chromium catalysts, methods for using the chromiumcatalysts to polymerize olefins, the polymer resins produced using suchchromium catalysts, and articles produced using these polymer resins.More particularly, the present disclosure relates to irradiating asupported hexavalent chromium catalyst with UV-visible light, andassociated catalyst preparation systems, polymerization reactor systems,and olefin polymerization processes.

BACKGROUND OF THE INVENTION

Chromium catalysts are among the most common catalysts used in olefinpolymerizations. Supported chromium catalysts often are prepared byimpregnating chromium onto a solid support, e.g., a solid oxide,followed by a calcining step. Generally, calcining is conducted in anoxidizing atmosphere, such that the chromium species within thesupported chromium catalyst can be converted to hexavalent chromium.

There are methods to reduce supported chromium catalysts to loweroxidations states, such as Cr(II), Cr(III), Cr(IV), and Cr(V), but suchmethods often require high temperature, reduce catalyst activity, andresult in polymers with poor melt index potential. It would bebeneficial to prepare reduced chromium catalysts that do not suffer fromthese deficiencies. Accordingly, it is to these ends that the presentinvention is generally directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

One aspect of the present invention is directed to catalyst preparationsystems that can comprise (a) a catalyst preparation vessel configuredto irradiate a slurry of a supported chromium catalyst in a diluent witha light beam at a wavelength in the UV-visible spectrum, (b) a catalystinlet configured to introduce the slurry of the supported chromiumcatalyst into the catalyst preparation vessel, wherein at least aportion of the chromium is in the hexavalent oxidation state, and (c) areduced catalyst outlet configured to withdraw a slurry of a reducedchromium catalyst from the catalyst preparation vessel. Polymerizationreactor systems incorporating the catalyst preparation systems also aredisclosed herein.

Methods for reducing a chromium catalyst for olefin polymerization areprovided in another aspect of the present invention. A representativemethod can comprise irradiating a reductant and a supported chromiumcatalyst comprising chromium in the hexavalent oxidation state with alight beam at a wavelength in the UV-visible spectrum to reduce at leasta portion of the supported chromium catalyst to form a reduced chromiumcatalyst.

Olefin polymerization processes are provided in yet another aspect ofthis invention, and such processes can comprise (I) irradiating areductant and a supported chromium catalyst comprising chromium in thehexavalent oxidation state with a light beam at a wavelength in theUV-visible spectrum to convert at least a portion of the supportedchromium catalyst to form a reduced chromium catalyst, and (II)contacting the reduced chromium catalyst and an optional co-catalystwith an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization reaction conditionsto produce an olefin polymer.

Reduced chromium catalysts and olefin polymers produced by therespective methods and processes also are encompassed herein.Unexpectedly, and beneficially, the reduced chromium catalysts can havea higher catalyst activity and/or productivity compared to chromiumcatalysts prepared without an irradiation step. Moreover, olefinpolymers described herein often are characterized by higher melt flowproperties and a narrower molecular weight distribution than olefinpolymers produced by processes using reduced chromium catalysts preparedwithout an irradiation step.

Ethylene-based polymers having an unexpected and beneficial combinationof properties also are disclosed herein. An ethylene polymer in oneaspect of this invention can be characterized by a ratio of Mw/Mn in arange from about 30 to about 110, a ratio of Mz/Mw in a range from about4 to about 10, and a CY-a parameter in a range from about 0.2 to about0.4. An ethylene polymer in another aspect of this invention can becharacterized by a ratio of Mw/Mn in a range from about 6 to about 15, aratio of Mz/Mw in a range from about 30 to about 70, and a melt index ina range from about 0.5 to about 10 g/10 min.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations can be provided inaddition to those set forth herein. For example, certain aspects can bedirected to various feature combinations and sub-combinations describedin the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates a schematic block diagram of a catalyst preparationsystem and polymerization reactor system consistent with aspects of thisinvention.

FIG. 2 presents a plot of the range of wavelengths emitted from red,blue, and violet LED diodes used to irradiate the supported chromiumcatalyst of Example 27.

FIG. 3 present a plot of the IR reflectance of a Cr/silica catalyst ofExample 28 calcined at 650° C.

FIG. 4 presents a plot of the molecular weight distributions of thepolymers of Examples 36, 40, and 42.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter can be described such that,within particular aspects, a combination of different features can beenvisioned. For each and every aspect and/or feature disclosed herein,all combinations that do not detrimentally affect the systems,compositions, processes, and/or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect and/or feature disclosed herein can be combined to describeinventive systems, compositions, processes, and/or methods consistentwith the present disclosure.

While systems, compositions, processes, and methods are described hereinin terms of “comprising” various components or steps, the systems,compositions, processes, and methods also can “consist essentially of”or “consist of” the various components or steps, unless statedotherwise.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “adiluent” or “a reductant” is meant to encompass one, or mixtures orcombinations of more than one, diluent or reductant, unless otherwisespecified. Generally, groups of elements are indicated using thenumbering scheme indicated in the version of the periodic table ofelements published in Chemical and Engineering News, 63(5), 27, 1985. Insome instances, a group of elements can be indicated using a common nameassigned to the group; for example, alkali metals for Group 1 elements,alkaline earth metals for Group 2 elements, transition metals for Group3-12 elements, and halogens or halides for Group 17 elements.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen, whethersaturated or unsaturated. Other identifiers can be utilized to indicatethe presence of particular groups in the hydrocarbon (e.g., halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon).The term “hydrocarbyl group” is used herein in accordance with thedefinition specified by IUPAC: a univalent group formed by removing ahydrogen atom from a hydrocarbon (that is, a group containing onlycarbon and hydrogen). Non-limiting examples of hydrocarbyl groupsinclude alkyl, alkenyl, aryl, and aralkyl groups, amongst other groups.

For any particular compound or group disclosed herein, any name orstructure presented is intended to encompass all structural isomers,conformational isomers, regioisomers, stereoisomers, and mixturesthereof that can arise from a particular set of substituents, unlessotherwise specified. The name or structure also encompasses allenantiomers, diastereomers, and other optical isomers (if there areany), whether in enantiomeric or racemic forms, as well as mixtures ofstereoisomers, as would be recognized by a skilled artisan, unlessotherwise specified. For example, a general reference to hexene (orhexenes) includes all linear or branched, acyclic or cyclic, hydrocarboncompounds having six carbon atoms and 1 carbon-carbon double bond;pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane;and a butyl group includes an n-butyl group, a sec-butyl group, aniso-butyl group, and a t-butyl group.

Unless otherwise specified, the term “substituted” when used to describea group, for example, when referring to a substituted analog of aparticular group, is intended to describe any non-hydrogen moiety thatformally replaces a hydrogen in that group, and is intended to benon-limiting. Also, unless otherwise specified, a group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Moreover, unless otherwise specified, “substituted” is intended to benon-limiting and include inorganic substituents or organic substituentsas understood by one of ordinary skill in the art.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and the like, as well as alloysand blends thereof. The term “polymer” also includes impact, block,graft, random, and alternating copolymers. A copolymer can be derivedfrom an olefin monomer and one olefin comonomer, while a terpolymer canbe derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers and terpolymers.Similarly, the scope of the term “polymerization” includeshomopolymerization, copolymerization, and terpolymerization. Therefore,an ethylene polymer would include ethylene homopolymers, ethylenecopolymers (e.g., ethylene/α-olefin copolymers), ethylene terpolymers,and the like, as well as blends or mixtures thereof. Thus, an ethylenepolymer encompasses polymers often referred to in the art as LLDPE(linear low density polyethylene) and HDPE (high density polyethylene).As an example, an ethylene copolymer can be derived from ethylene and acomonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer andcomonomer were ethylene and 1-hexene, respectively, the resultingpolymer can be categorized an as ethylene/1-hexene copolymer. The term“polymer” also includes all possible geometrical configurations, ifpresent and unless stated otherwise, and such configurations can includeisotactic, syndiotactic, and random symmetries.

Herein, ethylene polymers also encompass ethylene-based polymers havingnon-traditional terminal groups or chain ends. Traditional terminalgroups or chain ends include those that typically result (e.g.,saturated methyl chain ends, vinyl or vinylidene chain ends) from thepolymerization of ethylene, either alone or with alpha-olefincomonomers, such as 1-butene, 1-hexene, and 1-octene. Non-traditionalterminal groups or chain ends encompassed herein can include variousbranched alkane, cyclic alkane, aromatic, and halogenated hydrocarbongroups.

The term “contacting” is used herein to describe systems, compositions,processes, and methods in which the components are combined or reactedin any order, in any manner, and for any length of time, unlessotherwise specified. For example, the components can be contacted byblending or mixing, using any suitable technique.

A “soluble” material is meant to indicate that the material is dissolvedat standard temperature (25° C.) and pressure (1 atm); in this regard,there is no visual precipitation of the material in the solvent (e.g.,water or hydrocarbon solvent). Likewise, a “solution” is meant toindicate that there is no visual precipitate at standard temperature andpressure.

Various numerical ranges are disclosed herein. When a range of any typeis disclosed or claimed herein, the intent is to disclose or claimindividually each possible number that such a range could reasonablyencompass, including end points of the range as well as any sub-rangesand combinations of sub-ranges encompassed therein, unless otherwisespecified. As a representative example, the present applicationdiscloses, in certain aspects, that the chromium catalyst can have atotal pore volume in a range from about 0.9 to about 3 mL/g. By adisclosure that the chromium catalyst can have a total pore volume in arange from about 0.9 to about 3 mL/g, the intent is to recite that thetotal pore volume can be any amount within the range and, for example,can be equal to about 0.9, about 1.0, about 1.1, about 1.2, about 1.3,about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6,about 2.7, about 2.7, about 2.8, about 2.9, or about 3 mL/g.Additionally, the total pore volume can be within any range from about0.9 to about 3 mL/g (for example, the total pore volume can be in arange from about 1.2 to about 2.5 mL/g), and this also includes anycombination of ranges between about 0.9 and about 3 mL/g. Further, inall instances, where “about” a particular value is disclosed, then thatvalue itself is disclosed. Thus, the disclosure of a pore volume fromabout 0.9 to about 3 mL/g also discloses a pore volume range from 0.9 to3 mL/g (for example, from 1.2 to 2.5 mL/g), and this also includes anycombination of ranges between 0.9 and 3 mL/g. Likewise, all other rangesdisclosed herein should be interpreted in a manner similar to thisexample.

The term “about” means that amounts, sizes, formulations, parameters,and other quantities and characteristics are not and need not be exact,but can be approximate including being larger or smaller, as desired,reflecting tolerances, conversion factors, rounding off, measurementerrors, and the like, and other factors known to those of skill in theart. In general, an amount, size, formulation, parameter or otherquantity or characteristic is “about” or “approximate” whether or notexpressly stated to be such. The term “about” also encompasses amountsthat differ due to different equilibrium conditions for a compositionresulting from a particular initial mixture. Whether or not modified bythe term “about,” the claims include equivalents to the quantities. Theterm “about” can mean within 10% of the reported numerical value,preferably within 5% of the reported numerical value.

Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of theinvention, the typical methods and materials are herein described.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is generally directed to methods to reducechromium catalysts by irradiating supported hexavalent chromiumcatalysts with light in the presence of a reductant.

Catalyst preparation systems for reducing the supported hexavalentchromium catalysts, and olefin polymerizations using the reducedchromium catalysts, also are disclosed.

Methods for Reducing Chromium Catalysts

The methods to reduce chromium catalysts can comprise irradiating areductant and a supported chromium catalyst comprising chromium in thehexavalent oxidation state with a light beam at a wavelength in theUV-visible spectrum to reduce at least a portion of the supportedchromium catalyst to form a reduced chromium catalyst. The reducedchromium catalyst has an average oxidation state less than that of thesupported chromium catalyst. Reduced chromium catalysts produced by anymethods disclosed herein also are encompassed by this invention.

Generally, these methods are applicable to the reduction of any chromiumcatalyst, and are not limited to the reduction of any particular type ofsupported chromium catalyst. Thus, supported chromium catalystscontemplated herein encompass those prepared by contacting a solid oxidewith a chromium-containing compound—representative and non-limitingexamples of the chromium-compound compound include chromium (III)acetate, basic chromium (III) acetate, chromium (III) acetylacetonate,Cr₂(SO₄)₃, Cr(NO₃)₃, and CrO₃—and calcining in an oxidizing atmosphereto form a supported chromium catalyst. In these aspects, chromium can beimpregnated during, or prior to, the calcination step, which can beconducted at a variety of temperatures and time periods, and can begenerally selected to convert all or a portion of the chromium tohexavalent chromium. The irradiation methods disclosed herein cancomprise reducing at least a portion of the hexavalent chromium speciesto a reduced oxidation state—for instance, Cr(II), Cr(III), Cr(IV),and/or Cr(V) species, any of which may be catalytically active as anolefin polymerization catalyst—and the reduced catalyst can be used toproduce polymers with unexpected properties.

Any suitable chromium-containing compound (or chromium precursor) can beused as a chromium component to prepare the supported chromium catalyst.Illustrative and non-limiting examples of chromium (II) compounds caninclude chromium (II) acetate, chromium (II) chloride, chromium (II)bromide, chromium (II) iodide, chromium (II) sulfate, and the like, aswell as combinations thereof. Likewise, illustrative and non-limitingexamples of chromium (III) compounds can include a chromium (III)carboxylate, a chromium (III) naphthenate, a chromium (III) halide,chromium (III) sulfate, chromium (III) nitrate, a chromium (III)dionate, and the like, as well as combinations thereof. In some aspects,the chromium-containing compound can comprise chromium (III) acetate,chromium (III) acetylacetonate, chromium (III) chloride, chromium (III)bromide, chromium (III) sulfate, chromium (III) nitrate, and the like,as well combinations thereof.

While not required, it can be beneficial for the chromium-containingcompound to be soluble in a hydrocarbon solvent during catalystpreparation. In such situations, the chromium-containing compound cancomprise tertiary butyl chromate, a diarene chromium (0) compound,bis-cyclopentadienyl chromium (II), chromium (III) acetylacetonate,chromium acetate, and the like, or any combination thereof. Similarly,and not required, it can be beneficial for the chromium-containingcompound to be soluble in water during catalyst preparation. In suchsituations, the chromium-containing compound can comprise chromiumtrioxide, chromium acetate, chromium nitrate, and the like, or anycombination thereof.

Additionally, any suitable solid oxide can be used as a solid supportfor the supported chromium catalyst. Generally, the solid oxide cancomprise oxygen and one or more elements selected from Group 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or compriseoxygen and one or more elements selected from the lanthanide or actinideelements (See: Hawley's Condensed Chemical Dictionary, 11^(th) Ed., JohnWiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C. A., andBochmann, M., Advanced Inorganic Chemistry, 6^(th) Ed.,Wiley-Interscience, 1999). For example, the solid oxide can compriseoxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co,Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn,and Zr. Illustrative examples of solid oxide materials or compounds thatcan be used as solid support can include, but are not limited to, Al₂O₃,B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃,MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃,ZnO, ZrO₂, and the like, including mixed oxides thereof, andcombinations thereof.

The solid oxide can encompass oxide materials such as silica, “mixedoxide” compounds thereof such as silica-titania, and combinations ormixtures of more than one solid oxide material. Mixed oxides such assilica-titania can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used as solid oxide include, but are notlimited to, silica-alumina, silica-coated alumina, silica-titania,silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate,alumina-boria, silica-boria, aluminum phosphate, aluminophosphate,aluminophosphate-silica, titania-zirconia, and the like, or acombination thereof. In some aspects, the solid support can comprisesilica, silica-alumina, silica-coated alumina, silica-titania,silica-titania-magnesia, silica-zirconia, silica-magnesia, silica-boria,aluminophosphate-silica, and the like, or any combination thereof.Silica-coated aluminas are encompassed herein; such oxide materials aredescribed in, for example, U.S. Pat. No. 7,884,163, the disclosure ofwhich is incorporated herein by reference in its entirety.

The percentage of each oxide in a mixed oxide can vary depending uponthe respective oxide materials. As an example, a silica-aluminatypically has an alumina content from 5 wt. % to 95 wt. %. According toone aspect, the alumina content of the silica-alumina can be from 5 wt.% alumina 50 wt. % alumina, or from 8 wt. % to 30 wt. % alumina. Inanother aspect, high alumina content silica-alumina compounds can beemployed, in which the alumina content of these silica-alumina materialstypically ranges from 60 wt. % alumina to 90 wt. % alumina, or from 65wt. % alumina to 80 wt. % alumina.

In one aspect, the solid oxide can comprise silica-alumina,silica-coated alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminumphosphate, aluminophosphate, aluminophosphate-silica, titania-zirconia,or a combination thereof alternatively, silica-alumina; alternatively,silica-coated alumina; alternatively, silica-titania; alternatively,silica-zirconia; alternatively, alumina-titania; alternatively,alumina-zirconia; alternatively, zinc-aluminate; alternatively,alumina-boria; alternatively, silica-boria; alternatively, aluminumphosphate; alternatively, aluminophosphate; alternatively,aluminophosphate-silica; or alternatively, titania-zirconia.

In another aspect, the solid oxide can comprise silica, alumina,titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof,or any mixture thereof. In yet another aspect, the solid support cancomprise silica, alumina, titania, or a combination thereof;alternatively, silica; alternatively, alumina; alternatively, titania;alternatively, zirconia; alternatively, magnesia; alternatively, boria;or alternatively, zinc oxide. In still another aspect, the solid oxidecan comprise silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, silica-titania, silica-zirconia,alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria,silica-boria, aluminophosphate-silica, titania-zirconia, and the like,or any combination thereof.

The methods of reduction via irradiation that are disclosed herein canfurther comprise a step of calcining to form the supported chromiumcatalyst containing chromium in the hexavalent oxidation state. Thecalcination step can be conducted at a variety of temperatures and timeperiods, which are generally selected to convert all or a portion of thechromium to hexavalent chromium. Often, the calcination is performed inan oxidizing atmosphere, but this is not a requirement.

For instance, the calcination step can be conducted at a peaktemperature in a range from about 300° C. to about 1000° C.;alternatively, from about 500° C. to about 900° C.; alternatively, fromabout 600° C. to about 871° C.; alternatively, from about 550° C. toabout 870° C.; alternatively, from about 700° C. to about 850° C.;alternatively, from about 725° C. to about 900° C.; alternatively, fromabout 725° C. to about 871° C.; alternatively, from about 725° C. toabout 850° C.; alternatively, from about 750° C. to about 871° C.; oralternatively, from about 750° C. to about 850° C.

The duration of the calcination step is not limited to any particularperiod of time. Hence, this calcination step can be conducted, forexample, in a time period ranging from as little as 1 minute to as longas 12-24 hours, or more. In certain aspects, the calcination step can beconducted for a time period of from about 1 min to about 24 hr, fromabout 1 hr to about 12 hr, or from about 30 min to about 8 hr. Theappropriate calcination time can depend upon, for example, theinitial/peak temperature, among other variables.

While not being limited thereto, the supported chromium catalyst oftencan comprise chromium/silica, chromium/silica-titania,chromium/silica-titania-magnesia, chromium/silica-alumina,chromium/silica-coated alumina, chromium/aluminophosphate, and the like,or any combination thereof. In one aspect, the supported chromiumcatalyst can comprise chromium/silica, while in another aspect, thesupported chromium catalyst can comprise chromium/silica-titania. In yetanother aspect, the supported chromium catalyst can comprisechromium/silica-titania-magnesia; alternatively,chromium/silica-alumina; alternatively, chromium/silica-coated alumina;or alternatively, chromium/aluminophosphate.

Suitable modifications to the supported chromium catalyst also arecontemplated herein, and can include treatment with anelectron-withdrawing anion and/or a metal compound. Additionally, thesupported chromium compound can be subjected to the modifications at anytime during or after its preparation. For instance, in certain aspects,the solid support can be modified prior to impregnation with a chromiumcompound and/or a calcining step. In other aspects, the supportedchromium compound may be subjected to suitable modifications following acalcination step. In certain aspects, modifications can includesupported chromium catalysts, or components thereof, that have beenfluorided, chlorided, bromided, sulfated, or phosphated, and/or thosethat have been impregnated with metal ions (e.g., zinc, nickel,vanadium, titanium (titanated), silver, copper, gallium, tin, tungsten,molybdenum, zirconium, and the like, or combinations thereof).

Supported chromium catalysts that are treated with light as describedherein, and the resultant reduced chromium catalysts, can have anysuitable pore volume, surface area, and particle size. In certainaspects, the supported chromium catalyst (or the reduced chromiumcatalyst) can have a pore volume (total pore volume) in a range fromabout 0.5 to about 5 mL/g, from about 1 to about 5 mL/g, from about 0.9to about 3 mL/g, or from about 1.2 to about 2.5 mL/g. The surface areaof the catalyst is not limited to any particular range, and in certainaspects, the supported chromium catalyst (or the reduced chromiumcatalyst) can have a BET surface area in a range from about 100 to about1000 m²/g, from about 200 to about 700 m²/g, from about 100 to about 600m²/g, from about 250 to about 600 m²/g, from about 250 to about 550m²/g, or from about 275 to about 525 m²/g. Illustrative and non-limitingranges for the average (d₅₀) particle size of the supported chromiumcatalyst (or the reduced chromium catalyst) can include from about 10 toabout 500 microns, from about 25 to about 250 microns, from about 40 toabout 160 microns, or from about 40 to about 120 microns. BET surfaceareas are determined using the BET nitrogen adsorption method ofBrunauer et al., J. Am. Chem. Soc., 60, 309 (1938). Total pore volumesare determined in accordance with Halsey, G. D., J. Chem. Phys. (1948),16, pp. 931. The d50 particle size, or median or average particle size,refers to the particle size for which 50% of the sample has a smallersize and 50% of the sample has a larger size, and is determined usinglaser diffraction in accordance with ISO 13320.

The amount of chromium in the supported chromium catalyst (or thereduced chromium catalyst) is not particularly limited. Generally,however, the amount of chromium in the supported chromium catalyst (orthe reduced chromium catalyst) can range from about 0.01 to about 20 wt.%; alternatively, from about 0.1 to about 15 wt. %; alternatively, fromabout 0.1 to about 10 wt. %; alternatively, from about 0.2 to about 5wt. %; alternatively, from about 0.2 to about 2.5 wt. %; alternatively,from about 0.5 to about 10 wt. %; or alternatively, from about 1 toabout 6 wt. %. These weight percentages are based on the amount ofchromium relative to the total weight of the respective catalyst.

Similarly, before the reduction treatment, the supported the supportedchromium catalyst can have any suitable amount of chromium in itshexavalent state, relative to the total amount of chromium in thesupported chromium catalyst. In certain aspects, the portion of thechromium of the supported chromium catalyst in the hexavalent oxidationstate can be at least about 10 wt. %, at least about 20 wt. %, at leastabout 40 wt. %, at least about 60 wt. %, at least about 80 wt. %, atleast about 90 wt. %, at least about 95 wt. %, or at least about 99 wt.%, prior to irradiation.

Thus, in some aspects, before the reduction treatment, the amount ofchromium (VI) in the supported chromium catalyst can range from about0.01 to about 20 wt. %; alternatively, from about 0.1 to about 15 wt. %;alternatively, from about 0.1 to about 10 wt. %; alternatively, fromabout 0.2 to about 5 wt. %; alternatively, from about 0.2 to about 2.5wt. %; alternatively, from about 0.5 to about 10 wt. %; oralternatively, from about 1 to about 6 wt. %. These weight percentagesare based on the amount of chromium (VI) relative to the total weight ofthe supported chromium catalyst.

Generally, the irradiating step can be performed under any conditionssufficient to accommodate the irradiation of the reductant and thesupported hexavalent chromium catalyst with a light beam and to form thereduced chromium catalyst (having a lower oxidation state). Forinstance, the relative amount (or concentration) of the reductant to theamount of chromium (in the support chromium catalyst) can alter theefficacy of the reduction process. In certain aspects, the molar ratioof the reductant to the chromium (in the supported chromium catalyst)can be at least about 0.25:1, at least about 0.5:1, at least about 1:1,at least about 10:1, at least about 100:1, at least about 1000:1, or atleast about 10,000:1. Thus, a large excess of the reductant case beused, and there is no particular limit as to the maximum amount ofreductant.

Any reductants and/or diluents used in the irradiation methods disclosedherein can be chosen based on their suitability for downstream olefinpolymerization reactions. In one aspect, the reductant and the supportedchromium catalyst are irradiated at any suitable pressure, and thereductant is a diluent (or carrier) for the solid catalyst. Clearly, insuch circumstances, a large excess of reductant exists. In anotheraspect, a mixture of the reductant and the supported chromium catalystin a diluent is irradiated at any suitable pressure. In suchcircumstances, the reductant can be present in much lower amounts. Thus,the reductant can be separate from the diluent, or the reductant can bethe diluent. In either case, the diluent can be chosen based on itsutility and suitability to any of the olefin polymerizations processdescribed herein. Suitable diluents therefore can include certain olefinmonomers and comonomers and/or hydrocarbon solvents that are liquidsunder conditions appropriate for reduction via irradiation and/or forsubsequent olefin polymerization. Non-limiting examples of suitablehydrocarbon diluents that can be suitable as reductants can include,propane, isobutane, n-butane, n-pentane, isopentane, neopentane,n-hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, adamantane, decalin, ethylene, propylene, 1-butene,1-hexene, 1-octene, 1-decene, benzene, toluene, cyclohexene, xylene,ethylbenzene, and the like, or combinations thereof.

The temperature and pressure of the irradiating step can be such thatthe reductant and/or diluent remain(s) a liquid throughout reduction ofthe chromium catalyst. Advantageously, it was found that reducingsupported chromium compounds at lower temperatures than those typicallyrequired to reduce hexavalent chromium species using heat and not light,was possible by the irradiating steps disclosed herein. In certainaspects, the irradiating step can be conducted at a temperature of lessthan about 200° C., less than about 100° C., less than about 150° C.,less than about 40° C., from about 0° C. to about 200° C., from about 0°C. to about 100° C., or from about 10° C. to about 40° C., and canproduce a reduced chromium catalyst with excellent properties forsubsequent olefin polymerizations.

Generally, reductants suitable for the present invention can be any thatare capable of reducing at least a portion of the supported chromiumcompound upon exposure to light as described herein. In one aspect, thereductant can be present in the liquid phase, while in another aspect,the reductant can be present in the gas phase. Reductants (one or morethan one in combination) contemplated herein can encompass any compoundcomprising a C—H and/or H—H bond (H₂). In certain aspects, the reductantcan comprise one or more C—C bonds of any order (e.g., a single bond, adouble bond, a triple bond) such that almost any saturated orunsaturated hydrocarbon compound, containing exclusively C—H and C—Cbond bonds, can be suitable as a reductant for the methods, processes,and systems disclosed herein. In certain aspects, the reductant cancomprise a C₁ to C₃₆ hydrocarbon, a C₁ to Cis hydrocarbon, a C₁ to C₁₂hydrocarbon, and/or a C₁ to C₈ hydrocarbon. Additionally, reductantscontemplated herein can comprise a substituted and/or unsubstitutedhydrocarbon compound. In one aspect, the reductant can comprise analkane, an olefin, an aromatic, or any combination thereof (e.g., a C₁to C₃₆ alkane, olefin, and/or aromatic (up to 36 carbon atoms); a C₁ toC₁₈ alkane, olefin, and/or aromatic (up to 18 carbon atoms); a C₁ to C₁₂alkane, olefin, and/or aromatic (up to 12 carbon atoms); or a C₁ to C₈alkane, olefin, and/or aromatic (up to 8 carbon atoms)). The alkane canbe a linear alkane, a branched alkane, or a cyclic alkane. In anotheraspect, the reductant can comprise ethylene, 1-butene, 1-hexene,1-octene, methane, ethane, propane, isobutane, n-pentane, isopentane,n-hexane, tetrafluoroethane, cyclohexane, adamantane, decalin, benzene,toluene, and the like, or any combination thereof. In yet anotheraspect, the reductant can comprise a halogenated hydrocarbon(halogenated alkane, halogenated aromatic), where one or more halogenatoms replaces an equivalent number of hydrogen atoms in thehydrocarbon, provided that the compound contains a C—H bond.

The irradiating step may be further characterized by an amount of timethat the reductant and supported chromium catalyst are exposed to thelight beam, e.g., an exposure time. Without being bound by theory, it isbelieved that exposure to the light beam in the presence of a reductantis responsible for the reduction of the chromium catalyst, and thereforeit follows that the exposure time must be sufficient to allow thistransformation to occur, whether the transformation occurs very rapidlyor very slowly. Thus, in certain aspects, the exposure time can be in arange from about 15 sec to about 10 hr, from about 1 min to about 6 hr,from about 5 min to about 1 hr, from about 10 min to about 2 hr, fromabout 1 min to about 1 hr, or from about 1 min to about 15 min. As oneof skill in the art would recognize, the exposure time can vary based onthe intensity of the light beam.

However, it was unexpectedly determined in the examples that follow,that limiting the exposure time can be advantageous, which can formreduced chromium catalysts with increased catalytic activity and canproduce olefin polymers having improved melt index potential as comparedto chromium catalysts that underwent longer exposure times. In certainaspects, the exposure time can be less than about 1 min, less than about5 min, less than about 10 min, less than about 15 min, less than about30 min, less than about 1 hr, less than about 2 hr, or less than about 4hr.

In the disclosed methods, irradiation of a supported chromium catalystsample with a light beam in the UV-visible spectrum, in the presence ofa reductant, results in a chromium catalyst with a reduced oxidationstate. A wide range of wavelengths, light sources, and intensities canbe used, as long as these wavelengths, light sources, and intensitiesare sufficient to reduce at least a portion of the hexavalent chromiumspecies present in the supported chromium catalyst. In certain aspects,for instance, the light can be derived from any suitable source, such asfrom sunlight, a fluorescent white light, an LED diode, and/or a UVlamp. The distance from non-sunlight sources can be varied as needed(e.g., minimized) to increase the effectiveness of the irradiation.

The wavelength of the light can be any in the range of UV-visible light.In certain aspects, the wavelength of the light beam can be a singlewavelength, or more than one wavelength, such as a range of wavelengths.For instance, the wavelength of the light beam can be a range ofwavelengths spanning at least 25 nm, at least 50 nm, at least 100 nm, atleast 200 nm, or at least 300 nm. In one aspect, the wavelength of thelight beam can comprise a single wavelength or a range of wavelengths inthe UV spectrum, in the visible spectrum (from 380 nm to 780 nm), orboth. In another aspect, the wavelength of the light beam can comprise asingle wavelength or a range of wavelengths in the 200 nm to 750 nmrange. Yet, in another aspect, the wavelength of the light beam cancomprise a single wavelength or a range of wavelengths in the 300 to 750nm range, the 350 nm to 650 nm range, the 300 nm to 600 nm range, the300 nm to 500 nm range, or the 300 nm to 400 nm range. In other aspects,the wavelength of the light beam can comprise a single wavelength or arange of wavelengths below 600 nm, below 525 nm, or below 500 nm;additionally or alternatively, above 350 nm, above 400 nm, or above 450nm.

The light beam of the irradiating step also can be characterized by itsintensity (e.g., the total amount of light emitted from a source). Incertain aspects, the light beam can have an intensity of at least about500 lumens, at least about 1,000 lumens, at least about 2,000 lumens atleast about 5,000 lumens, at least about 10,000 lumens, at least about20,000 lumens, at least about 50,000 lumens, or at least about 100,000lumens. Thus, there may not be an upper limit on the intensity of thelight source. Alternatively, the light beam can have an intensity in arange from about 50 to about 50,000 lumens, from about 50 to about10,000 lumens, from about 100 to about 5,000 lumens, or from about 500to about 2,000 lumens. Additionally, the light beam can be characterizedby the amount of light reaching the reductant and supported chromiumcatalyst, i.e., the flux. In certain aspects, the reductant and thesupported chromium catalyst comprising chromium in the hexavalentoxidation state can be irradiated by at least about 100 lux, at leastabout 500 lux, at least about 1000 lux, at least about 2000 lux, atleast about 5000 lux, at least about 10,000 lux, at least about 20,000lux, at least about 100,000 lux, or in a range from about 10,000 toabout 1,000,000 lux, from about 50,000 to about 500,000 lux, or about50,000 to about 200,000 lux. Additionally or alternatively, in certainaspects, the reductant and the supported chromium catalyst comprisingchromium in the hexavalent oxidation state can be irradiated with alight beam having a power of at least about 50 watts, at least about 100watts, at least about 200 watts, at least about 500 watts, at leastabout 1,000 watts, or at least about 2,000 watts.

The efficacy of the methods of reduction via irradiation that aredisclosed herein can be characterized by the chemical composition of thereduced chromium catalyst, as compared to the supported chromiumcatalyst starting material. In particular, the reduced chromiumcatalysts can have a significant portion of the chromium species fromthe supported chromium catalyst reduced during the irradiation step, andcan have high catalytic activity. In certain aspects, at least about 10wt. %, at least about 20 wt. %, at least about 40 wt. %, at least about60 wt. %, at least about 80 wt. %, at least about 90 wt. %, at leastabout 95 wt. %, or at least about 99 wt. %, of the supported chromiumcatalyst (or the hexavalent species in the supported chromium catalyst)can be reduced to form the reduced chromium catalyst.

Thus, in the reduced chromium catalyst, less than or equal to about 75wt. % of the chromium can be in the hexavalent state in one aspect,while less than or equal to about 50 wt. % of the chromium can be in thehexavalent state in another aspect, and less than or equal to about 40wt. % of the chromium can be in the hexavalent state in yet anotheraspect, and less than or equal to about 30 wt. % of the chromium can bein the hexavalent state in still another aspect. These values are basedon the total amount of chromium in the reduced chromium catalyst.

Additionally or alternatively, the chromium in the reduced chromiumcatalyst can be characterized by an average valence of less than orequal to about 5.25. More often, the chromium in the reduced chromiumcatalyst has an average valence of less than or equal to about 5;alternatively, an average valence of less than or equal to about 4.75;alternatively, an average valence of less than or equal to about 4.5;alternatively, an average valence of less than or equal to about 4.25;or alternatively, an average valence of less than or equal to about 4.

Additionally, the efficacy of the methods disclosed herein can becharacterized by the relative activity of the reduced chromium catalystin an olefin polymerization reaction. In certain aspects, the reducedchromium catalyst can have a catalyst activity greater (e.g., at least10%, at least 20%, at least 50%, at least 80%, etc., greater) than thatof the supported chromium catalyst (which has no light irradiationtreatment, or exposure to light but with no reductant present, etc.).Additionally or alternatively, the reduced chromium catalyst (viairradiation with a reductant) can be compared to an otherwise identicalcatalyst—calcined with the same temperature and procedure—but thentreated with the same reductant at an elevated temperature (e.g., 300°C., 350° C., 400° C., 450° C., or 500° C.) so as to cause reduction fromthermal means in the absence of light. Thus, the reduced chromiumcatalyst can have a catalyst activity greater (e.g., at least 10%, atleast 20%, at least 50%, at least 80%, etc., greater) than that of anotherwise identical catalyst prepared using the same reductant at anelevated temperature without light irradiation. These activitycomparisons are under the same polymerization conditions, which areslurry polymerization conditions at a temperature of 105° C. and apressure of 550 psig.

Catalyst Preparation Systems

In another aspect of this invention, a catalyst preparation system isprovided, and in this aspect, the catalyst preparation system cancomprise (a) a catalyst preparation vessel configured to irradiate aslurry of a supported chromium catalyst in a diluent with a light beamat a wavelength in the UV-visible spectrum, (b) a catalyst inletconfigured to introduce the slurry of the supported chromium catalystinto the catalyst preparation vessel, wherein at least a portion of thechromium is in the hexavalent oxidation state, and (c) a reducedcatalyst outlet configured to withdraw a slurry of a reduced chromiumcatalyst from the catalyst preparation vessel.

Generally, the features of any of the catalyst preparation systemsdisclosed herein (e.g., the catalyst preparation vessel, the light beam,the catalyst inlet, and the reduced catalyst outlet, among others) areindependently described herein, and these features can be combined inany combination to further describe the disclosed catalyst preparationsystems. Moreover, other devices or catalyst preparation systemcomponents can be present in the disclosed catalyst preparation systems,unless stated otherwise. For instance, the catalyst preparation systemcan further include a co-catalyst inlet configured to introduce anysuitable co-catalyst feed stream into the catalyst preparation vessel.Additionally or alternatively, the catalyst preparation system canfurther include a reductant inlet configured to introduce any suitablereductant feed stream into the catalyst preparation vessel. Thus, thereductant can be fed separately to the catalyst preparation vessel.Additionally or alternatively, the diluent can contain the reductant, orthe diluent can be the reductant.

The catalyst preparation system can be configured to operate in acontinuous manner, for instance, to provide a continuous feed stream ofthe reduced chromium catalyst to a polymerization reactor via thereduced catalyst outlet of the catalyst preparation system.Alternatively, the catalyst preparation system can be configured forbatchwise production. Indeed, the catalyst preparation vessel itself isnot limited to any particular type, and typically can be a stirred tank,a flow reactor vessel, or other suitable tank or vessel. The catalystpreparation vessel can be configured to operate at any temperature andpressure suitable for irradiating the slurry of the chromium catalyst.

Whether configured for batchwise or continuous production, the catalystpreparation system can be configured for any residence time sufficientto irradiate the slurry of the supported chromium catalyst, while alsosupplying a sufficient amount of the reduced catalyst to any downstreamor subsequent process, e.g., a polymerization process. Suitableresidence times can be the same or different from (e.g., longer than)the exposure times disclosed hereinabove for the irradiating step of themethods for reducing a chromium catalyst. In certain aspects, the systemcan be configured for a residence time of from about 15 sec to about 10hr, from about 1 min to about 6 hr, from about 5 min to about 1 hr, fromabout 10 min to about 2 hr, from about 1 min to about 1 hr, or fromabout 1 min to about 15 min.

Encompassed herein are aspects of this invention in which the source ofthe light beam is sunlight. However, in aspects where the light sourceis an artificial light source, e.g., a UV lamp, a fluorescent whitelight, and/or an LED diode, the catalyst preparation system can furthercomprise a lamp assembly to house the light source and facilitateirradiation of the supported chromium catalyst within the catalystpreparation vessel. The lamp assembly can be inside of, or outside of,the catalyst preparation vessel. For a lamp assembly inside the catalystpreparation vessel, the lamp assembly can be positioned within thereaction space of the vessel, such that the slurry comprising thesupported chromium catalyst and the diluent (which can be the reductant)or the slurry, diluent, and reductant, can flow around the lampassembly, which can be housed within a quartz tube or other suitablebarrier to shield the lamp from direct contact with the slurry and thesolid chromium catalyst. A non-limiting example of this configuration isshown in U.S. Patent Publication No. 2014/0221692, directed to flowreactor vessels and reactor systems, incorporated herein by reference inits entirety.

Alternatively, the lamp assembly can be positioned outside of thecatalyst preparation vessel. Thus, the catalyst preparation vessel cancomprise a window or screen to allow light emitted from the lamp to passinto the catalyst preparation vessel and irradiate (e.g., reduce) thesupported chromium catalyst and reductant therein. The lamp assembly canbe configured to emit a light beam at any wavelength or range ofwavelengths in the UV-visible spectrum, as disclosed hereinabove for theirradiating step of the methods for reducing a chromium catalyst.

The catalyst preparation system can further comprise (d) a controllerthat is configured to control the residence time of the supportedchromium catalyst in the catalyst preparation vessel, and/or thetemperature of the catalyst preparation vessel, and/or the intensity ofthe light beam, and/or the wavelength of the light beam, and/or theamount of the reduced chromium catalyst, and/or the molar ratio of thereductant to chromium. The controller also can be configured to controla flow rate of the slurry entering the catalyst inlet and the flow rateexiting the reduced catalyst outlet. If a co-catalyst is fed to thecatalyst preparation vessel, the controller can be further configured tocontrol a flow rate of the co-catalyst feed stream. Similarly, if areductant is fed to the catalyst preparation vessel (and separate fromthe diluent), the controller can be further configured to control a flowrate of the reductant feed stream entering the catalyst preparationvessel.

As a non-limiting example, if the molar ratio of the reductant tochromium in the catalyst preparation vessel is below a target value(i.e., too low), then the controller can decrease the flow rate of theslurry (containing the supported chromium catalyst) entering the vesseland/or increase the flow rate of the reductant feed stream entering thevessel.

A representative catalyst preparation system consistent with aspects ofthis invention is illustrated in FIG. 1. The catalyst preparation system100 includes a catalyst preparation vessel 110, a supported chromiumcatalyst inlet 101, and a reduced catalyst outlet 115. A reactor 120also is shown in FIG. 1 to demonstrate that the catalyst preparationsystems disclosed herein can be integrated as part of a polymerizationreactor system, such as any of those described herein. The catalystpreparation system 100 also includes co-catalyst inlet 103 configured tointroduce a co-catalyst feed stream into the catalyst preparation vessel(if desired), and a reductant inlet 105 to introduce a reductant feedstream into the catalyst preparation vessel (if desired). Alternatively,the reductant can be present in the supported chromium catalyst feedstream, entering the vessel 110 via inlet 101. Additional inlets andfeed streams to the catalyst preparation vessel also can be present,though separate feed streams to the catalyst preparation vessel are notshown. Lamp assembly 130 is shown as positioned inside or outside thecatalyst preparation vessel, and able to irradiate within vessel 110.FIG. 1 also shows a process parameter 132 (e.g., temperature, residencetime, relative amount of reductant, etc.) from the catalyst preparationvessel 110 can be relayed to a measurement system 140 for determinationof various process and operating conditions within vessel 110. A processparameter 134 from the reduced catalyst outlet 115 (e.g., flow rate,amount of reduced catalyst, etc.), and/or a process parameter 136 fromthe reactor 120, can be submitted to the measurement system 140.

Information or data 145 from the measurement system 140 can be providedto controller 150, which can then control or adjust 155 a flow rate ofmaterial within any of inlet 101, inlet 103, inlet 105, and outlet 115.Alternatively, or additionally, controller 150 can independently controlor adjust 155 various process or operating conditions—e.g., thetemperature, the residence time, the relative amount of reductant, thelight intensity, the light wavelength, etc.—of the catalyst preparationvessel 110.

Polymerization Reactor Systems and Processes

Encompassed herein are polymerization reactor systems, and in an aspectof this invention, the polymerization reactor systems can comprise anyof the catalyst preparation systems disclosed herein, and a reactorconfigured to contact the reduced chromium catalyst with an olefinmonomer and an optional olefin comonomer under polymerization conditionsto produce an olefin polymer. Polymerization processes also areencompassed herein, and in another aspect of this invention, thepolymerization process can comprise (I) irradiating a reductant and asupported chromium catalyst comprising chromium in the hexavalentoxidation state with a light beam at a wavelength in the UV-visiblespectrum to reduce at least a portion of the supported chromium catalystto form a reduced chromium catalyst, and (II) contacting any reducedchromium catalyst disclosed herein (e.g., a reduced chromium catalystprepared by any method for reducing chromium catalysts disclosed above)and an optional co-catalyst with an olefin monomer and an optionalolefin comonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer. Any of the features of step (I)can be the same as those described herein (e.g., the reductant, thesource of the light beam, the wavelength, etc.) for the methods ofreducing a supported chromium catalyst.

Beneficially, employing the irradiation step to form the reducedcatalyst (prior to initiating polymerization) can result in a more fullyactivated catalyst, which has been reduced and alkylated, beforeentering the polymerization reactor. The resulting overall activityincrease (the catalyst no longer requires reduction/alkylation afterentering the polymerization reactor) can allow for the use of lesscatalyst and lower polymerization temperatures, which in turn can reducepolymer swelling and fouling, and improve overall operating efficiency.

Unsaturated monomers that can be employed with catalyst compositions andpolymerization processes of this invention typically can include olefincompounds having from 2 to 30 carbon atoms per molecule and having atleast one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂ o alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof; alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

The chromium catalysts of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. The polymerization conditions for the variousreactor types are well known to those of skill in the art. Gas phasereactors can comprise fluidized bed reactors or staged horizontalreactors. Slurry reactors can comprise vertical or horizontal loops.High pressure reactors can comprise autoclave or tubular reactors. Thesereactor types generally can be operated continuously. Continuousprocesses can use intermittent or continuous polymer product discharge.Polymerization reactor systems and processes also can include partial orfull direct recycle of unreacted monomer, unreacted comonomer, and/ordiluent (e.g., the same or different from the diluent used duringreduction of the chromium catalyst).

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). For instance, the polymerization reactor system can comprisea solution reactor, a gas-phase reactor, a slurry reactor, or acombination of two or more of these reactors. Production of polymers inmultiple reactors can include several stages in at least two separatepolymerization reactors interconnected by a transfer device making itpossible to transfer the polymer resulting from the first polymerizationreactor into the second reactor. The polymerization conditions in one ofthe reactors can be different from the operating conditions of the otherreactor(s). Alternatively, polymerization in multiple reactors caninclude the manual transfer of polymer from one reactor to subsequentreactors for continued polymerization. Multiple reactor systems caninclude any combination including, but not limited to, multiple loopreactors, multiple gas phase reactors, a combination of loop and gasphase reactors, multiple high pressure reactors, or a combination ofhigh pressure with loop and/or gas phase reactors. The multiple reactorscan be operated in series, in parallel, or both. Accordingly, thepresent invention encompasses polymerization reactor systems comprisinga single reactor, comprising two reactors, and comprising more than tworeactors. The polymerization reactor system can comprise a slurryreactor, a gas-phase reactor, a solution reactor, in certain aspects ofthis invention, as well as multi-reactor combinations thereof.

According to one aspect, the polymerization reactor system can compriseat least one loop slurry reactor, e.g., comprising vertical orhorizontal loops. Monomer, diluent, catalyst, and optional comonomer canbe continuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and8,822,608, each of which is incorporated herein by reference in itsentirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used, such as can be employed in the bulkpolymerization of propylene to form polypropylene homopolymers.

According to yet another aspect, the polymerization reactor system cancomprise at least one gas phase reactor (e.g., a fluidized bed reactor).Such reactor systems can employ a continuous recycle stream containingone or more monomers continuously cycled through a fluidized bed in thepresence of the catalyst under polymerization conditions. A recyclestream can be withdrawn from the fluidized bed and recycled back intothe reactor. Simultaneously, polymer product can be withdrawn from thereactor and new or fresh monomer can be added to replace the polymerizedmonomer. Such gas phase reactors can comprise a process for multi-stepgas-phase polymerization of olefins, in which olefins are polymerized inthe gaseous phase in at least two independent gas-phase polymerizationzones while feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790,5,436,304, 7,531,606, and 7,598,327, each of which is incorporated byreference in its entirety herein.

According to still another aspect, the polymerization reactor system cancomprise a high pressure polymerization reactor, e.g., can comprise atubular reactor or an autoclave reactor. Tubular reactors can haveseveral zones where fresh monomer, initiators, or catalysts are added.Monomer can be entrained in an inert gaseous stream and introduced atone zone of the reactor. Initiators, catalysts, and/or catalystcomponents can be entrained in a gaseous stream and introduced atanother zone of the reactor. The gas streams can be intermixed forpolymerization.

Heat and pressure can be employed appropriately in such high pressurepolymerization reactors to obtain optimal polymerization reactionconditions.

According to yet another aspect, the polymerization reactor system cancomprise a solution polymerization reactor, wherein themonomer/comonomer can be contacted with the catalyst composition bysuitable stirring or other means. A carrier comprising an inert organicdiluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone can be maintained at temperatures(e.g., up to between 150° C. and 180° C.) and pressures that will resultin the formation of a solution of the polymer in a reaction medium.Agitation can be employed to obtain better temperature control and tomaintain uniform polymerization mixtures throughout the polymerizationzone. Adequate means are utilized for dissipating the exothermic heat ofpolymerization.

In some aspects, the polymerization reactor system can comprise anycombination of a raw material feed system, a feed system for catalystand/or catalyst components, and/or a polymer recovery system, includingcontinuous systems. In other aspects, suitable reactor systems cancomprise systems for feedstock purification, catalyst storage andpreparation, extrusion, reactor cooling, polymer recovery,fractionation, recycle, storage, loadout, laboratory analysis, andprocess control, in addition to or as part of the catalyst preparationsystems disclosed herein.

The catalyst compositions and/or polymerization processes disclosedherein often can employ a co-catalyst. In some aspects, the co-catalystcan comprise a metal hydrocarbyl compound, examples of which includenon-halide metal hydrocarbyl compounds, metal hydrocarbyl halidecompounds, non-halide metal alkyl compounds, metal alkyl halidecompounds, and so forth, and in which the metal can be any suitablemetal, often a group 13 metal. Hence, the metal can be boron or aluminumin certain aspects of this invention, and the co-catalyst can comprise aboron hydrocarbyl or alkyl, or an aluminum hydrocarbyl or alkyl, as wellas combinations thereof.

In one aspect, the co-catalyst can comprise an aluminoxane compound, anorganoaluminum compound, or an organoboron compound, and this includescombinations of more than co-catalyst compound. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propyl-aluminoxane, n-butylaluminoxane, t-butyl-aluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentyl-aluminoxane,2-pentylaluminoxane, 3-pentyl-aluminoxane, isopentyl-aluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoaluminums includetrimethylaluminum, triethylaluminum, tri-n-propyl aluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or any combinationthereof. Representative and non-limiting examples of organoboronsinclude tri-n-butyl borane, tripropylborane, triethylborane, and thelike, or any combination thereof. Co-catalysts that can be used in thecatalyst compositions of this invention are not limited to theco-catalysts described above. Other suitable co-catalysts (such asorganomagnesiums and organolithiums) are well known to those of skill inthe art including, for example, those disclosed in U.S. Pat. Nos.3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983,7,294,599 7,601,665, 7,884,163, 8,114,946, and 8,309,485, which areincorporated herein by reference in their entirety.

Polymerization conditions that can be monitored, adjusted, and/orcontrolled for efficiency and to provide desired polymer properties caninclude, but are not limited to, reactor temperature, reactor pressure,catalyst flow rate into the reactor, monomer flow rate (and comonomer,if employed) into the reactor, monomer concentration in the reactor,olefin polymer output rate, recycle rate, hydrogen flow rate (ifemployed), reactor cooling status, and the like.

Polymerization temperature can affect catalyst productivity, polymermolecular weight, and molecular weight distribution. A suitablepolymerization temperature can be any temperature below thede-polymerization temperature according to the Gibbs Free energyequation. Typically, this includes from about 60° C. to about 280° C.,for example, from about 60° C. to about 185° C., from about 60° C. toabout 120° C., or from about 130° C. to about 180° C., depending uponthe type of polymerization reactor, the polymer grade, and so forth. Insome reactor systems, the polymerization reactor temperature generallycan be within a range from about 70° C. to about 110° C., or from about125° C. to about 175° C. Various polymerization conditions can be heldsubstantially constant, for example, for the production of a particulargrade of olefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor typically can be less than 1000 psig (6.9 MPa). Thepressure for gas phase polymerization usually can be in the 200 psig to500 psig range (1.4 MPa to 3.4 MPa). High pressure polymerization intubular or autoclave reactors generally can be conducted at about 20,000psig to 75,000 psig (138 MPa to 517 MPa). Polymerization reactors canalso be operated in a supercritical region occurring at generally highertemperatures and pressures (for instance, above 92° C. and 700 psig(4.83 MPa)). Operation above the critical point of apressure/temperature diagram (supercritical phase) can offer advantagesto the polymerization reaction process.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting areduced chromium catalyst and an optional co-catalyst with an olefinmonomer and optionally an olefin comonomer in a polymerization reactorsystem under polymerization conditions to produce an olefin polymer, andwherein the polymerization process is conducted in the absence of addedhydrogen (no hydrogen is added to the polymerization reactor system). Asone of ordinary skill in the art would recognize, hydrogen can begenerated in-situ by certain catalyst systems in various olefinpolymerization processes, and the amount generated can vary dependingupon the specific catalyst components employed, the type ofpolymerization process used, the polymerization reaction conditionsutilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a reduced chromium catalyst and an optionalco-catalyst with an olefin monomer and optionally an olefin comonomer ina polymerization reactor system under polymerization conditions toproduce an olefin polymer, wherein the polymerization process isconducted in the presence of added hydrogen (hydrogen is added to thepolymerization reactor system). For example, the ratio of hydrogen tothe olefin monomer in the polymerization process can be controlled,often by the feed ratio of hydrogen to the olefin monomer entering thereactor. The amount of hydrogen added (based on the amount of olefinmonomer) to the process can be controlled at a molar percentage whichgenerally falls within a range from about 0.05 to about 20 mole %, fromabout 0.1 to about 15 mole %, from about 0.25 to about 10 mole %, orfrom about 0.5 to about 10 mole %. In some aspects of this invention,the feed or reactant ratio of hydrogen to olefin monomer can bemaintained substantially constant during the polymerization run for aparticular polymer grade. That is, the hydrogen:olefin monomer ratio canbe selected at a particular ratio, and maintained at the ratio to withinabout +/−25% during the polymerization run. Further, the addition ofcomonomer (or comonomers) can be, and generally is, substantiallyconstant throughout the polymerization run for a particular polymergrade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

As discussed above, a representative polymerization reactor systemconsistent with aspects of this invention is illustrated in FIG. 1. Thepolymerization reactor system encompasses the catalyst preparationsystem 100 (comprising a catalyst preparation vessel 110, a lampassembly 130, a measurement system 140, and a controller 150) and areactor 120. The catalyst preparation system 100 functions as describedabove. Process parameters 132, 134, 136 are relayed to the measurementsystem 140 for determination of various process and operatingconditions, and the measurement system 140, therefore, can any encompassany suitable measurement device or equipment (e.g., a flow meter, athermocouple, etc.) for identifying particular process and operatingconditions within catalyst preparation vessel 110, reduced catalystoutlet 115, and/or reactor 120. As above, the polymerization reactorsystem includes a reduced catalyst outlet 115 configured to withdraw aslurry of a reduced chromium catalyst from catalyst preparation vessel110 and feed into the reactor 120.

Polymers and Articles

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and optional comonomer(s) described herein. Forexample, the olefin polymer can comprise an ethylene homopolymer, anethylene copolymer (e.g., ethylene/α-olefin, ethylene/1-butene,ethylene/1-hexene, ethylene/1-octene, etc.), a propylene homopolymer, apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including any combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the olefin polymers (e.g., ethylene polymers) of thisinvention, whose typical properties are provided below.

An illustrative and non-limiting example of an ethylene polymer (e.g.,an ethylene homopolymer and/or ethylene copolymer) consistent with thepresent invention can have a ratio of Mw/Mn in a range from about 30 toabout 110, a ratio of Mz/Mw in a range from about 4 to about 10, and aCY-a parameter in a range from about 0.2 to about 0.4. Other suitableranges for the ratio of Mw/Mn of the ethylene polymer include from about35 to about 105, from about 40 to about 100, from about 45 to about 95,or from about 50 to about 90. Likewise, other suitable ranges for theratio of Mz/Mw include from about 5 to about 9, from about 5 to about 8,from about 5.5 to about 7.5, or from about 6 to about 7. Additionally,other suitable ranges for the CY-a parameter include from about 0.23 toabout 0.38, from about 0.25 to about 0.35, or from about 0.27 to about0.34. Moreover, the ethylene polymer can be further characterized by aMn in a range from about 3,000 to about 12,000 g/mol, from about 4,000to about 11,000 g/mol, from about 4,000 to about 10,000 g/mol, fromabout 5,000 to about 10,000 g/mol, or from about 5,500 to about 9,500g/mol. Additionally or alternatively, the ethylene polymer can have a Mwin a range from about 250,000 to about 700,000 g/mol, from about 300,000to about 675,000 g/mol, from about 350,000 to about 625,000 g/mol, orfrom about 375,000 to about 600,000 g/mol. Additionally oralternatively, the ethylene polymer can have a HLMI of less than orequal to about 10, less than or equal to about 8, less than or equal toabout 5, or less than or equal to about 4 g/10 min. Additionally oralternatively, the ethylene polymer can be characterized by a number oflong chain branches (LCBs) from about 0.5 to about 4, from about 0.5 toabout 3, from about 0.7 to about 2.8, or from about 1 to about 2.5 LCBsper million total carbon atoms.

Another illustrative and non-limiting example of an ethylene polymerconsistent with the present invention can have a ratio of Mw/Mn in arange from about 6 to about 15, a ratio of Mz/Mw in a range from about30 to about 70, and a melt index in a range from about 0.5 to about 10g/10 min. Other suitable ranges for the ratio of Mw/Mn include fromabout 7 to about 14, from about 8 to about 13, from about 8 to about 12,or from about 9 to about 10. Likewise, other suitable ranges for theratio of Mz/Mw include from about 35 to about 65, from about 40 to about60, from about 45 to about 55, or from about 47 to about 51.Additionally, other suitable ranges for the melt index include fromabout 0.5 to about 5, from about 0.7 to about 7, or from about 1 toabout 5 g/10 min. Moreover, the ethylene polymer can be furthercharacterized by a Mn in a range from about 10,000 to about 25,000g/mol, from about 13,000 to about 22,000 g/mol, from about 15,000 toabout 20,000 g/mol, or from about 16,000 to about 18,000 g/mol.Additionally or alternatively, the ethylene polymer can have a Mw in arange from about 100,000 to about 400,000 g/mol, from about 100,000 toabout 300,000 g/mol, from about 110,000 to about 250,000 g/mol, or fromabout 140,000 to about 200,000 g/mol. Additionally or alternatively, theethylene polymer can be characterized by a less than or equal to about2, less than or equal to 1, less than or equal to about 0.8, less thanor equal to about 0.5, or less than or equal to about 0.2 LCBs permillion total carbon atoms.

If not already specified, these illustrative and non-limiting examplesof ethylene polymers consistent with the present invention also can haveany of the polymer properties listed below and in any combination.

Olefin polymers (e.g., ethylene homopolymers and/or copolymers) producedin accordance with some aspects of this invention generally can have amelt index (MI) from 0 to about 100 g/10 min. Melt indices in the rangefrom 0 to about 50 g/10 min, from 0 to about 25 g/10 min, or from 0 toabout 10 g/10 min, are contemplated in other aspects of this invention.For example, a polymer of the present invention can have a melt index ina range from 0 to about 5, from 0 to about 3, from 0 to about 1, or from0 to about 0.5 g/10 min.

Olefin polymers produced in accordance with this invention can have ahigh load melt index (HLMI) of less than or equal to about 200, lessthan or equal to about 150, or less than or equal to about 100 g/10 min.Suitable ranges for the HLMI can include, but are not limited to, from 0to about 150, from about 2 to about 120, from about 1 to about 100, fromabout 1 to about 80, from about 2 to about 80, from about 4 to about 60,from about 8 to about 60, from about 1 to about 50, from about 4 toabout 50, from about 3 to about 40, or from about 6 to about 40 g/10min.

Olefin polymers produced in accordance with this invention also can becharacterized by their melt index properties relative to olefin polymersproduced using a comparable (otherwise identical) catalysts preparedwithout an irradiation step (e.g., a reduced chromium catalyst can beprepared by using a heating step to reduce hexavalent chromium species;the supported chromium catalyst without reduction; etc.). In certainaspects, the MI (or HLMI) of the olefin polymer produced by the processcan be greater than 50% of, greater than 80% of, greater than 90% of,greater than 100% of, greater than 120% of, greater than 150% of, orgreater than 200% of, the MI (or HLMI) of an olefin polymer obtainedwithout the irradiating step, under the same polymerization conditions.

The densities of olefin polymers produced using the chromium catalystsand the processes disclosed herein often are greater than or equal toabout 0.89 g/cm³. In one aspect of this invention, the density of theolefin polymer can be in a range from about 0.89 to about 0.96 g/cm³.Yet, in another aspect, the density can be in a range from about 0.91 toabout 0.95 g/cm³, such as, for example, from about 0.91 to about 0.94g/cm³, from about 0.92 to about 0.955 g/cm³, or from about 0.93 to about0.955 g/cm³.

In an aspect, olefin polymers described herein can have a weight-averagemolecular weight (Mw) in a range from about 50,000 to about 2,000,000,from about 50,000 to about 1,000,000, from about 50,000 to about700,000, from about 75,000 to about 500,000, from about 100,000 to about500,000, from about 100,000 to about 400,000, or from about 150,000 toabout 300,000 g/mol.

In an aspect, olefin polymers described herein can have a number-averagemolecular weight (Mn) in a range from about 2,000 to about 250,000, fromabout 2,000 to about 100,000, from about 2,000 to about 50,000, fromabout 5,000 to about 200,000, from about 5,000 to about 150,000, or fromabout 5,000 to about 50,000 g/mol. In another aspect, olefin polymersdescribed herein can have a Mn in a range from about 10,000 to about100,000, from about 10,000 to about 75,000, from about 25,000 to about150,000, or from about 50,000 to about 150,000 g/mol.

Olefin polymers, whether homopolymers, copolymers, and so forth, can beformed into various articles of manufacture. Articles which can comprisepolymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Also contemplated herein is a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a chromium catalyst (e.g., produced as describedherein) and an optional co-catalyst with an olefin monomer and anoptional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer; and (ii)forming an article of manufacture comprising the olefin polymer (e.g.,having any of the polymer properties disclosed herein). The forming stepcan comprise blending, melt processing, extruding, molding, orthermoforming, and the like, including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, modifications, and equivalentsthereof which, after reading the description herein, may suggestthemselves to one of ordinary skill in the art without departing fromthe spirit of the present invention or the scope of the appended claims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2.16 kg weight, I₁₀ (g/10 min) was determined inaccordance with ASTM D1238 at 190° C. with a 10 kg weight, and high loadmelt index (HLMI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 21.6 kg weight. BET surface areas can be determinedusing the BET nitrogen adsorption method of Brunaur et al., J. Am. Chem.Soc., 60, 309 (1938). Total pore volumes can be determined in accordancewith Halsey, G. D., J. Chem. Phys. (1948), 16, pp. 931.

In these examples, supported chromium catalysts comprising hexavalentchromium species were irradiated under UV-visible light in the presenceof various reductants and under various treatment conditions. Prior toirradiation, the supported chromium catalysts were calcined at thespecified temperature in dry air (an oxidizing atmosphere) in afluidized bed for three hours, in order to convert the chromium speciesto their respective hexavalent oxidation state.

For each of the examples provided below, about two grams of thesupported catalyst were first charged to an air-tight glass container at25° C., optionally in the presence of a reductant. The glass containerwas then exposed to light as noted in Tables I-IV below. For exampleswhere the glass container was exposed to sunlight, the container wastaken outside and placed in direct sunlight, slowly rotating thecontainer to ensure even exposure of the supported chromium catalystmixture. For examples where the glass container was exposed toartificial light, the sample was placed in a box containing afluorescent light emitting light in the UV-Vis spectrum. Examples notexposed to light were stored under dim lighting, or wrapped in foil toensure no light entered the glass container. Reduction of the supportedchromium catalysts was monitored by the presence of a color change. Foreach catalyst, the starting hexavalent supported chromium catalyst hadan orange color which darkened significantly upon exposing the catalystto light in the presence of a reductant, indicating reduction of thesupported chromium catalyst starting material.

The reduced chromium catalysts, prepared as described above, were usedin polymerization experiments conducted in a 2-L stainless-steelautoclave reactor containing 1.2 L of isobutane as a diluent. Thepolymerization reactions were conducted in the dark, and ethylene wasfed on demand to maintain a reactor pressure of 550 psig. The reactorwas maintained at the 105° C. (unless otherwise specified) throughoutthe experiment by an automated heating-cooling system. Forcopolymerization experiments, 1-hexene was flushed in with the initialethylene charge. At the end of each experiment, the resulting polymerwas dried at 60° C. under reduced pressure.

Examples 1-20

Examples 1-20 employed a supported chromium catalyst comprisingsilica-titania (2.5 wt. % Ti and 1.0 wt. % Cr). The Cr/silica-titaniacatalyst had a BET surface area of 500 m²/g, a pore volume of 2.5 mL/g,and an average particle size of 130 μm. The Cr/silica-titania catalystswere calcined at 850° C. (except as indicated otherwise) in dry air (anoxidizing atmosphere) in order to convert the respective chromiumspecies to the hexavalent oxidation state. Tables I-II summarize thevarious catalyst reductions, catalyst productivity (grams ofpolyethylene per gram of catalyst), catalyst activity (grams ofpolyethylene per gram of catalyst per hour), and resultant polymer HLMI,I₁₀, and MI (g/10 min).

Comparative Examples 1-6 describe attempts to reduce the hexavalentchromium present on the Cr/silica-titania catalysts without exposing thecatalyst to light in the presence of a reductant. As shown in Examples1-2, when no reductant was present, the catalyst was unaffected by light(orange). In contrast, Examples 9-20 each underwent a color changefollowing exposure to light after as little as 10 minutes in thepresence of various reductants, the color change persisting after beingremoved from the light. Unexpectedly, when a reductant was present, evenshort exposures of light resulted in a color change, indicatingreduction of the chromium to a lower valence chromium species. In fact,the catalyst activity and melt index potential of the catalysts wereimproved by relatively short exposures to light, as shown by InventiveExamples 9, 13, and 17.

In addition to reductions with ethylene, the reduction step wassurprisingly effective for hydrocarbons that are relatively difficult tooxidize, such as methane and benzene. Examples 3-6 demonstrate thedifficulty of reducing Cr(VI) catalysts in the presence of thehydrocarbon methane using conventional methods. In Examples 3-6, methanewas passed through the catalysts in a fluidized bed (without light), andrequired heating to 350° C. and above (Examples 4-6) before a colorchange was observed. In contrast, and unexpectedly, exposing samples ofthe catalyst to sunlight in the presence of methane, without heating,induced a color change in the catalyst mixture within minutes (Example13). Even more surprising, reduction in the presence of methane by theinventive method was not accompanied by a significant loss in catalystactivity and melt index potential, indicating that the catalyst producedin the presence of light is fundamentally distinct from that produced byconventional methods. Note the higher catalyst activities and melt indexproperties of Examples 13-14 as compared to Examples 3-6.

Examples 15-17 provide additional examples of reductions using compoundsthat are traditionally poor reductants, including tetrafluoroethane andbenzene. Each example demonstrated a distinct and quick color changeupon exposure to light. The use of benzene resulted in increasedcatalyst activity and comparable melt index properties to ComparativeExamples 1-2.

Inventive Examples 18-19 were conducted using H₂ as the reductant.Surprisingly, the reduction produced an active catalyst within minuteshaving increased MI potential and comparable activity, relative to theComparative Example 7. This result is unexpected, particularly becausethermal reduction in hydrogen typically results in a relatively inactivecatalyst with low MI potential.

Comparative Example 8 is provided as direct comparison for Example 20,where the Cr/silica-titania catalyst was calcined at slightly elevatedtemperatures (871° C.), prior to being reduced in the presence ofmethane for 6 hr. The resulting reduced Cr/silica-titania catalysts wereused in an ethylene/1-hexene copolymerization reaction, andsurprisingly, both the catalyst activity and melt index properties ofthe catalyst reduced in the presence of light were higher than theCr(VI)/silica-titania catalyst of Comparative Example 8.

TABLE I Comparative Examples 1-8 using Cr/silica-titania without lightreduction Productivity Activity HLMI I₁₀ MI Example Reductant TreatmentColor (gPE/gCat) (g/g/h) (g/10 min) (g/10 min) (g/10 min) 1 None None, 1orange 2315 3307 110 27.2 1.97 week 2 None light, orange 2434 3319 9623.7 1.75 1 week 3 methane none orange 3087 3705 39 8.7 0.55 (300° C.) 4methane none green 2209 3488 28 6.5 0.46 (350° C.) 5 methane none green1823 3646 22 5.2 0.32 (400° C.) 6 methane none green 2338 2646 17 3.80.23 (450° C.) 7* none none orange 2919 3434 47 10.3 0.64 8*^(†) nonenone orange 3095 12379 62 14.2 0.91 *The catalyst was calcined at atemperature of 871° C. ^(†)The polymerization reaction was conducted at100° C. in the presence of 5 mL 1-hexene.

TABLE II Inventive Examples 9-20 using Cr/silica-titania with lightreduction Productivity Activity HLMI I₁₀ MI Example Reductant TreatmentColor (gPE/gCat) (g/g/h) (g/10 min) (g/10 min) (g/10 min)  9 10 psigsunlight, blue/gray 2980 5430 88 23.1 1.72 ethylene 10 min 10 12 psigsunlight, blue/gray 2231 2434 71 17.6 1.38 ethylene 4 h 11 12 psigsunlight, blue/gray 2443 3858 57 14.6 1.10 ethylene 4 h 12 10 psigsunlight blue/gray 2212 2328 30 7.1 0.50 ethylene 6 h, 3 h (x2) 13 10psig sunlight, green 2915 6780 114 26.3 1.95 methane 10 min 14 10 psigsunlight, green 3099 5469 70 16.7 1.17 methane 6 h 15 10 psig sunlight,green 1554 1636 29 7.1 0.54 Freon 2 h 16 10 psig sunlight, green 28201945 29 7.0 0.55 Freon 2 h 17 4 drops sunlight red/violet 3951 5268 8920.8 1.46 benzene 15 min 18* 10 psig sunlight, green 3297 2953 52 11.90.88 H₂ 15 min 19* 10 psig sunlight gray/green 3437 3124 31 7.3 0.50 H₂2 h 20*^(†) 10 psig sunlight green 3239 14951 67 14.7 0.92 methane 6 h*The catalyst was calcined at a temperature of 871° C. ^(†)Thepolymerization reaction was conducted at 100° C. in the presence of 5 mL1-hexene.

Examples 21-26

Examples 21-26 employed a Cr/silica catalyst as the supported catalystcomprising a hexavalent chromium species (1.0 wt. % Cr). The Cr/silicacatalysts were calcined at 650° C. in dry air (an oxidizing atmosphere)in order to convert the chromium to the hexavalent oxidation state. TheCr/silica catalyst had a BET surface area of 500 m²/g, a pore volume of1.6 mL/g, and an average particle size of 100 μm. Table III summarizesvarious catalyst reductions, catalyst productivity (grams ofpolyethylene per gram of catalyst), catalyst activity (grams ofpolyethylene per gram of catalyst per hour), and resultant polymer HMLI,I10, and MI (g/10 min).

Using ethylene as the reductant, Examples 22-23 demonstrated comparablecatalyst activity to Example 21, but an unexpected improvement in meltindex potential. Also unexpectedly, the catalysts prepared with themethane reductant in sunlight resulted in a significant increase incatalyst activity, comparable melt index potential in ethylenehomopolymerization (Example 24), and superior melt index potential inethylene/1-hexene copolymerization (Example 26).

TABLE III Examples using Cr/Silica Catalysts Productivity Activity HLMII₁₀ MI Ex. Reductant Treatment Color (gPE/gCat) (g/g/h) (g/10 min) (g/10min) (g/10 min) 21 none none orange 2347 2996 4.8 0.82 0.009 22 10 psigsunlight blue/gray 1409 3019 6.1 1.22 — ethylene (x2) 6 h, 3 h 23 10psig sunlight blue/gray 1814 1432 7.4 1.53 0.033 ethylene (x2) 6 h, 3 h24 10 psig sunlight, green 2603 4222 4.0 0.66 — methane 6 h 25^(†) nonenone orange 2923 5480 2.4 0.21 0    26^(†) 10 psig sunlight, green 30947140 3.6 0.60 0.014 methane 6 h ^(†)The polymerization reaction wasconducted at 100° C. in the presence of 5 mL 1-hexene.

Examples 27-29

Certain examples above were conducted in sunlight or alternatively,under a fluorescent light emitting a spectrum of UV-Visible light. Inorder to evaluate which wavelength of light may be most effective atreducing the hexavalent species, Cr/silica-titania catalyst as describedabove was prepared by calcining for 3 h at 650° C., and treating thecalcined catalyst with a small amount (0.5 mL) of n-hexane in Example27. Samples of the catalyst underwent a reduction step as conductedabove, using one of a red LED (631 nm), blue LED (450 nm), or violet LED(392 nm) in glass bottles. The intensity and wavelength distribution ofeach light source is shown in FIG. 2. The color of each sample wasmonitored as an indicator of progress and efficiency of the reductionstep. Of the three, the blue light was by far the most effective,whereas the red light achieved almost nothing. The violet light was alsoeffective, but somewhat less so than the blue light. Since theseexperiments were conducted in glass containers that may absorb theshortest wavelengths of visible light, it is believed that a significantportion of the light emitted from the violet LED may have been absorbedby the glass.

In Example 28, IR reflectance spectra were obtained for a Cr/silicasample prepared as described above for Examples 21-26. As is shown inFIG. 3, the spectra demonstrate a strong absorbance at about 600 nmattributable to Cr(III) species, and another absorbance at about 340 nmattributable to Cr(VI) species. Thus, while not wishing to be bound bytheory, a more effective light source for catalyst reduction shouldinclude wavelengths less than 500 nm (e.g., compare blue light versusred light in FIG. 2).

For Example 29, perfluorohexane was evaluated as a reductant in a mannersimilar to benzene (Example 17), but did not result in a color change.Perfluorohexane contains only C—F and C—C bonds. While not wishing to bebound by theory, it is believed that compounds with C—H bonds are moresusceptible to oxidation under irradiation conditions.

Examples 30-45

Examples 30-45 were performed in the same manner as Examples 1-20 and,with the exception of Examples 36 and 42, used the same supportedchromium catalyst comprising silica-titania (2.5 wt. % Ti and 1.0 wt. %Cr). The Cr/silica-titania catalysts were calcined at 871° C. in dryair. Examples 36 and 42 used a 10% Cr/silica catalyst that was calcinedat 400° C. in dry air for 3 hr. Catalyst weights ranged from 0.04 to0.26 grams and polymerization reaction times ranged from 30 to 240 forExamples 30-45. Table IV summarizes the various catalyst reductions,catalytic activity, polymer molecular weight properties, polymerrheological characterization, and polymer MI, I₁₀, and HLMI (g/10 min).

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 200 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mnis the number-average molecular weight, Mw is the weight-averagemolecular weight, Mz is the z-average molecular weight, My isviscosity-average molecular weight, and Mp is the peak molecular weight(location, in molecular weight, of the highest point of the molecularweight distribution curve).

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on anAnton Paar MCR 501 rheometer using parallel-plate geometry. Allrheological tests were performed at 190° C. The complex viscosity |η*|versus frequency (ω) data were then curve fitted using the modifiedthree parameter Carreau-Yasuda (CY) empirical model to obtain the zeroshear viscosity—η₀, characteristic viscous relaxation time—τ_(η), andthe breadth parameter—a (CY-a parameter). The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{{\eta^{*}(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$

wherein: |η*(ω)|=magnitude of complex shear viscosity;

-   -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η) in sec);    -   a=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters can be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

The long chain branches (LCBs) per 1,000,000 total carbon atoms of theoverall polymer were calculated using the method of Janzen and Colby (J.Mol. Struct., 485/486, 569-584 (1999), incorporated herein by referencein its entirety), from values of zero shear viscosity (determined fromthe Carreau-Yasuda (CY) model), and measured values of Mw obtained usinga Dawn EOS multiangle light scattering detector (Wyatt).

As shown in Table IV, the light reduction step was surprisinglyeffective for several different hydrocarbon reductants: methane, ethane,n-pentane, n-hexane, toluene, decalin, adamantane, and cyclohexane.Example 34 (34 min) and Example 35 (91 min) used differentpolymerization times, as did Example 43 (61 min) and Example 44 (37min). With the exception of Examples 36 and 42, the catalysts hadsurprising catalytic activity and melt index potential. Examples 30-33in Table IV demonstrate that catalyst treatment with light irradiationin the presence of a reductant reduces the long chain branching contentof the polymer produced, with an unexpected increase in the CY-aparameter.

FIG. 4 illustrates the molecular weight distributions of the polymers ofExamples 36, 40, and 42. As shown in Table IV and FIG. 4, the polymersof Example 36 (0.26 g catalyst, 151 min reaction time) and Example 42(0.2 g catalyst, 240 min reaction time), unexpectedly, had very broadmolecular weight distributions (Mw/Mn in the 50-90 range) in combinationwith relatively high CY-a values (0.29-0.33), and very low levels ofLCBs (less than 3 per million total carbon atoms). Also surprisingly,Table IV and FIG. 4 demonstrate that the polymer of Example 40 (0.057 gcatalyst, 57 min reaction time) had a long high molecular weight tail,resulting in a Mz/Mw value in the 45-50 range, despite have a relativelynarrow molecular weight distribution (Mw/Mn less than 10), andsubstantially no LCBs.

TABLE IV Examples 30-45 Productivity Activity HLMI I₁₀ MI ExampleReductant Treatment Color (gPE/gCat) (g/g/h) (g/10 min) (g/10 min) (g/10min) CY-a 30 None None — — — — — 4.45 0.199 31 None None — — — — — 0.160.193 32 n-pentane Sunlight blue/gray 3188 3298 154 36.4 3.65 0.226 1 h33 n-hexane White light blue/gray 2251 2936 139 32.8 3.22 0.219 3 h 34toluene Blue light blue/black 1481 3065 203 46.8 3.6 0.199 1.5 h 35toluene Blue light blue/black 4235 3434 67 15.2 1.1 0.201 1.5 h 36n-pentane UV light black 238 107 3.4  0.5 — 0.294 3 h 37 10 psig UVlight dark blue/ 2267 2616 113 26.8 2.1 0.196 ethane 4 h gray 38 tolueneBlue light black 2312 2070 153 33.4 2.9 0.205 2.5 h 39 decalin Bluelight blue 1954 2345 198 34.7 4.2 0.204 2 h 40 adamantane Blue lightblue 2205 2646 166 30.6 3.5 0.200 2 h 41 cyclohexane Blue light blue2423 1069 47  7.3 0.8 0.210 2 h 42 None None dark red 262 81 0.5 — —0.327 43 methane Blue light green 2692 2884 157 36.5 3.4 0.229 2 h 44methane Blue light blue/gray 1024 1920 82 18.6 1.5 0.174 2 h 45 NoneNone orange 2668 2541 220 51.7 4.6 0.219

TABLE IV Examples 30-45 (continued) Mn Mw Mz η₀ τ_(η) J-C LCB ExampleReductant (kg/mol) (kg/mol) (kg/mol) Mw/Mn Mz/Mw (Pa-sec) (sec) (per MMC) 30 None — — — — — — — — 31 None — — — — — — — — 32 n-pentane 14.7 100579 6.8 5.8 9.68E+03 0.016 8.8 33 n-hexane 9.8 102 962 10.3 9.5 1.24E+040.022 9.9 34 toluene 11.1 107 1060 9.6 9.9 1.24E+04 0.020 7.8 35 toluene14.3 142 1129 9.9 8.0 4.42E+04 0.081 6.4 36 n-pentane 8.3 416 2810 50.36.8 4.11E+06 50.4 2.2 37 ethane 9.6 120 1159 12.5 9.6 2.29E+04 0.034 7.738 toluene 14.7 101 760 6.9 7.5 1.26E+04 0.020 10.3 39 decalin 14.4 108835 7.5 7.7 9.74E+03 0.014 5.9 40 adamantane 17.2 166 8076 9.6 48.61.20E+04 0.015 <0.01 41 cyclohexane 15.7 162 1453 10.4 9.0 5.23E+040.111 4.2 42 None 6.3 557 3342 88.5 6.0 7.01E+06 49.6 1.2 43 methane13.8 104 726 7.5 7.0 8.20E+03 0.014 6.2 44 methane 14.3 130 1165 9.1 9.03.31E+04 0.024 7.4 45 None 12.9 102 843 7.9 8.3 8.01E+03 0.013 6.6

Examples 46-52

Examples 46-52 were performed to determine the extent of reduction ofthe hexavalent chromium and the average valence after reduction in arepresentative supported chromium catalyst. Table V summarizes theresults. Example 52 was a chromium/silica-titania catalyst containingapproximately 0.8 wt. % chromium and 7 wt. % titania, and having a BETsurface area of 530 m²/g, a pore volume of 2.6 mL/g, and an averageparticle size of 130 um, which was calcined in dry air at 850° C. for 3hr to convert chromium to the hexavalent oxidation state (orange). Thisconverted over 86 wt. % of the chromium into the hexavalent state. ForExamples 46-47, approximate 2 g samples of the catalyst of Example 52were separately charged to a glass reaction vessel and 0.5 mL of liquidisopentane was charged to the vessel. For Examples 48-49, about 1.5 atmof gaseous methane was charged to the glass bottle. Then, the bottle wasplaced in a light-proof box under blue fluorescent light (approximately2 times the intensity expected from sunlight), and the bottle wascontinuously rotated so that all of the catalyst was exposed to thelight for 24 hr. The final catalyst color is noted in Table V.Afterward, into the bottle, along with the catalyst, was introducedabout 20 mL of a solution of 2 M H₂SO₄. To this was added 5 drops offerroin Fe(+3) indicator. This usually turned a blue-green colorindicating the presence of Fe(III) ions. Next, the solution was titratedto the ferroin endpoint (red color) using a solution of ferrous ammoniumsulfate, which had been previously calibrated by reaction with astandardized 0.1 M sodium dichromate solution. When the solution turnedred, the end point was signaled, and the titrant volume was recorded, tocalculate the oxidation capacity of the catalyst, expressed as wt. %Cr(VI) and as percent reduced, that is, the percent of the originalCr(VI) oxidative power that has been removed by the reduction treatment.The average valence was also computed by multiplying the percent reducedby +3 and subtracting that number from +6.

Of course, this treatment gives only an average oxidation state. Notethat although Table V lists the oxidative power measured as wt. %Cr(VI), in reality all of the chromium could be present in lower valencestates, such as Cr(IV) or Cr(V). Thus, the Cr(VI) value in Table V onlylists the maximum amount of Cr(VI) that could be present. More likely,the reduced catalysts have a combination of several valence states thatproduce the measured oxidative power. Note that some of the reducedchromium, and particularly those catalysts reduced with CO, may be inthe divalent state, which would not have been detected in this test,which stops in the trivalent state.

Example 52 demonstrates that the air-calcined chromium catalystcontained substantially most of its chromium (0.69/0.80=86 wt. %)present as Cr(VI), and it is this Cr(VI) amount that is being reduced inthe light treatment. Therefore, this amount of Cr(VI) serves as thestarting amount, which had an average valence of +6, and which serves asa reference, to which the reduced catalysts are then compared. Examples46-47 were reduced chromium catalysts with an average valence ofapproximately +3.3, with no more than 0.06 wt. % Cr(VI), and with lessthan 10 wt. % of the starting hexavalent chromium still remaining in thehexavalent oxidation state. Examples 48-49 were reduced chromiumcatalysts with an average valence of approximately +4.1, with no morethan 0.26 wt. % Cr(VI), and with less than 40 wt. % of the chromium inthe hexavalent oxidation state. For Examples 50-51, the catalyst wasreduced in CO with either blue light or elevated temperature, resultingin no oxidative power being measured (0 wt. % Cr(VI) in the table).Thus, the average valence must be no more than +3. But the catalyst thatwas CO-reduced by conventional means (Example 51) is known to have avalence of mostly Cr(II), which is not detected in this test.Accordingly, Examples 50 and 51 are listed as less than or equal to +3.Notably, this test cannot distinguish between Cr(II) and Cr(III)species, but there was no measurable amount of hexavalent chromium inExamples 50-51.

TABLE V Examples 46-52 Catalyst Cr(VI) Reduced Average Example ReductantTreatment Color (g) (wt. %) (wt. %) Valence 46 isopentane Blue lightblue 2.05 0.06 90.8 3.28 24 hr 47 isopentane Blue light blue 2.08 0.0690.9 3.27 24 hr 48 methane Blue light olive 2.14 0.26 62.3 4.13 24 hrgreen 49 methane Blue light olive 2.30 0.26 61.9 4.14 24 hr green 50 COBlue light blue 2.33 0.00 100 <3 2 hr green 51 CO CO reduction blue 2.520.00 100 <3 30 min - 350° C. 52 None None orange — 0.69 0 6.00

The invention is described above with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the above detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A method for reducing a chromium catalyst for olefinpolymerization, the method comprising irradiating a reductant and asupported chromium catalyst comprising chromium in the hexavalentoxidation state with a light beam at a wavelength in the UV-visiblespectrum to reduce at least a portion of the supported chromium catalystto form a reduced chromium catalyst.

Aspect 2. The method defined in aspect 1, wherein the method comprisesirradiating a mixture of the supported chromium catalyst and thereductant in a diluent at any suitable pressure.

Aspect 3. The method defined in aspect 2, wherein the diluent comprisesany suitable hydrocarbon solvent or any hydrocarbon solvent disclosedherein, e.g., 1-hexene, hexanes, isobutane, toluene, or cyclohexene, aswell as mixtures or combinations thereof.

Aspect 4. The method defined in any one of the preceding aspects,wherein the supported chromium catalyst comprises any suitable solidoxide or any solid oxide disclosed herein, e.g., silica, alumina,silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, etc., or any combinationthereof.

Aspect 5. The method defined in any one of aspects 1-3, wherein thesupported chromium catalyst comprises silica, silica-alumina,silica-coated alumina, silica-titania, silica-titania-magnesia,silica-zirconia, silica-magnesia, silica-boria, aluminophosphate-silica,etc., or any combination thereof.

Aspect 6. The method defined in any one of aspects 1-3, wherein thesupported chromium catalyst comprises chromium/silica,chromium/silica-titania, chromium/silica-titania-magnesia,chromium/silica-alumina, chromium/silica-coated alumina,chromium/aluminophosphate, etc., or any combination thereof.

Aspect 7. The method defined in any one of the preceding aspects,wherein the catalyst has a total pore volume in any suitable range orany range disclosed herein, e.g., from about 0.5 to about 5 mL/g, fromabout 1 to about 5 mL/g, from about 0.9 to about 3 mL/g, from about 1.2to about 2.5 mL/g, etc.

Aspect 8. The method defined in any one of the preceding aspects,wherein the catalyst has a BET surface area in any suitable range or anyrange disclosed herein, e.g., from about 100 to about 1000 m²/g, fromabout 200 to about 700 m²/g, from about 250 to about 600 m²/g, fromabout 275 to about 525 m²/g, etc.

Aspect 9. The method defined in any one of the preceding aspects,wherein the catalyst further comprises any suitable modification or anymodification disclosed herein, e.g., titanated, fluorided, sulfated,phosphated, etc.

Aspect 10. The method defined in any one of the preceding aspects,further comprising a step of calcining to form the supported chromiumcatalyst comprising chromium in the hexavalent oxidation state, whereincalcining comprises any suitable peak temperature and time conditions orany peak temperature and time conditions disclosed herein, e.g., a peaktemperature from about 300° C. to about 1000° C., from about 500° C. toabout 900° C., from about 550° C. to about 870° C., etc., for a timeperiod of from about 1 min to about 24 hr, from about 1 hr to about 12hr, from about 30 min to about 8 hr, etc.

Aspect 11. The method defined in any one of the preceding aspects,wherein the supported chromium catalyst (or reduced chromium catalyst)comprises any suitable amount of chromium or any amount disclosedherein, e.g., from about 0.01 to about 20 wt. %, from about 0.1 to about10 wt. %, from about 0.2 to about 5 wt. %, from about 0.2 to about 2.5wt. %, etc., based on the weight of the catalyst.

Aspect 12. The method defined in any one of the preceding aspects,wherein the wavelength comprises a single wavelength or a range ofwavelengths in the visible spectrum.

Aspect 13. The method defined in any one of aspects 1-11, wherein thewavelength comprises a single wavelength or a range of wavelengths inthe 200 nm to 750 nm range.

Aspect 14. The method defined in any one of aspects 1-11, wherein thewavelength comprises a single wavelength or a range of wavelengths inthe 300 to 750 nm range, the 350 nm to 650 nm range, the 300 nm to 500nm range, or the 300 nm to 400 nm range.

Aspect 15. The method defined in any one of aspects 1-11, wherein thewavelength comprises a single wavelength or a range of wavelengths below600 nm, below 525 nm, or below 500 nm.

Aspect 16. The method defined in any one of the preceding aspects,wherein the wavelength is a single wavelength.

Aspect 17. The method defined in any one of aspects 1-15, wherein thewavelength is a range of wavelengths spanning at least 25 nm, at least50 nm, at least 100 nm, at least 200 nm, etc.

Aspect 18. The method defined in any one of the preceding aspects,wherein the irradiating step is conducted at any suitable temperature orany temperature disclosed herein, e.g., less than about 200° C., lessthan about 100° C., less than about 40° C., from about 0° C. to about100° C., from about 10° C. to about 40° C., etc.

Aspect 19. The method defined in any one of the preceding aspects,wherein the irradiating step is conducted for any suitable exposure timeor for any exposure time disclosed herein, e.g., from about 15 sec toabout 10 hr, from about 1 min to about 6 hr, from about 1 min to about15 min, from about 5 min to about 1 hr, etc.

Aspect 20. The method defined in any one of the preceding aspects,wherein the light beam has any suitable intensity or an intensity in anyrange disclosed herein, e.g., at least about 500 lumens, at least about1000 lumens, at least about 2000 lumens, at least about 5000 lumens, atleast about 10,000 lumens, at least about 20,000 lumens, etc.

Aspect 21. The method defined in any one of the preceding aspects,wherein the light beam has any suitable power or any power disclosedherein, e.g., at least about 50 watts, at least about 100 watts, atleast about 200 watts, at least about 500 watts, at least about 1,000watts, at least about 2,000 watts, etc.

Aspect 22. The method defined in any one of the preceding aspects,wherein the supported chromium catalyst is irradiated with any suitableilluminance or any illuminance disclosed herein, e.g., at least about100 lux, at least about 500 lux, at least about 1000 lux, at least about2000 lux, at least about 5000 lux, at least about 10,000 lux, at leastabout 20,000 lux, at least about 100,000 lux, etc.

Aspect 23. The method defined in any one of the preceding aspects,wherein the portion of the chromium of the supported chromium catalystin the hexavalent oxidation state is at least about 10 wt. %, at leastabout 20 wt. %, at least about 40 wt. %, at least about 60 wt. %, atleast about 80 wt. %, at least about 90 wt. %, etc., and/or the portionof the chromium of the reduced chromium catalyst in the hexavalentoxidation state is less than or equal to about 75 wt. %, less than orequal to about 50 wt. %, less than or equal to about 40 wt. %, less thanor equal to about 30 wt. %, etc.

Aspect 24. The method defined in any one of the preceding aspects,wherein the chromium in the reduced chromium catalyst has an averagevalence of less than or equal to about 5.25, less than or equal to about5, less than or equal to about 4.75, less than or equal to about 4.5,less than or equal to about 4.25, less than or equal to about 4, etc.

Aspect 25. The method defined in any one of the preceding aspects,wherein the reduced chromium catalyst has a catalyst activity greater(by any amount disclosed herein, e.g., at least 10%, at least 20%, atleast 50%, etc.) than that of the supported chromium catalyst, underslurry polymerization conditions at a temperature of 105° C. and apressure of 550 psig, and/or the reduced chromium catalyst has acatalyst activity greater (by any amount disclosed herein, e.g., atleast 10%, at least 20%, at least 50%, etc.) than that of an otherwiseidentical catalyst prepared using the same reductant at an elevatedtemperature (e.g., 300° C., 350° C., 400° C., 450° C., or 500° C.)without light irradiation, under slurry polymerization conditions at atemperature of 105° C. and a pressure of 550 psig.

Aspect 26. A reduced chromium catalyst prepared by the method of any oneof the preceding aspects.

Aspect 27. A catalyst preparation system comprising:

(a) a catalyst preparation vessel configured to conduct the method forreducing a chromium catalyst defined in any one of aspects 1-25;

(b) a catalyst inlet configured to introduce a slurry of the supportedchromium catalyst into the catalyst preparation vessel, wherein at leasta portion of the chromium is in the hexavalent oxidation state; and

(c) a reduced catalyst outlet configured to withdraw a slurry of areduced chromium catalyst from the catalyst preparation vessel.

Aspect 28. A catalyst preparation system comprising:

(a) a catalyst preparation vessel configured to irradiate a slurry of asupported chromium catalyst in a diluent with a light beam at awavelength in the UV-visible spectrum;

(b) a catalyst inlet configured to introduce the slurry of the supportedchromium catalyst into the catalyst preparation vessel, wherein at leasta portion of the chromium is in the hexavalent oxidation state; and

(c) a reduced catalyst outlet configured to withdraw a slurry of areduced chromium catalyst from the catalyst preparation vessel.

Aspect 29. The system defined in aspect 27 or 28, wherein the diluentcomprises any suitable reductant or any reductant disclosed herein,e.g., substituted or unsubstituted hydrocarbons, saturated orunsaturated hydrocarbons, etc.

Aspect 30. The system defined in any one of aspects 27-29, wherein thecatalyst preparation system further comprises a reductant inletconfigured to introduce a feed stream of a reductant into the catalystpreparation vessel.

Aspect 31. The system defined in any one of aspects 27-30, wherein thecatalyst preparation vessel is any suitable vessel or any vesseldisclosed herein, e.g., a stirred tank, a flow reactor vessel, etc.

Aspect 32. The system defined in any one of aspects 27-31, wherein thecatalyst preparation system is configured to operate batchwise orcontinuously.

Aspect 33. The system defined in any one of aspects 27-32, wherein theslurry of the supported chromium catalyst is irradiated for any suitableresidence time (or exposure time) or for any duration disclosed herein,e.g., from about 15 sec to about 10 hr, from about 1 min to about 6 hr,from about 1 min to about 15 min, from about 5 min to about 1 hr, etc.

Aspect 34. The system defined in any one of aspects 27-33, wherein thecatalyst preparation system further comprises a lamp assembly inside oroutside the catalyst preparation vessel.

Aspect 35. The system defined in any one of aspects 27-34, wherein thecatalyst preparation vessel comprises any suitable source or any sourcedisclosed herein, e.g., sunlight, a fluorescent white light, a UV lamp,etc., for the light beam.

Aspect 36. The system defined in any one of aspects 27-35, wherein thecatalyst preparation system further comprises a co-catalyst inletconfigured to introduce a co-catalyst feed stream into the catalystpreparation vessel.

Aspect 37. The system defined in any one aspects 27-36, wherein thecatalyst preparation system further comprises (d) a controllerconfigured to control the residence time of the supported chromiumcatalyst in the catalyst preparation vessel, and/or the temperature ofthe catalyst preparation vessel, and/or the intensity of the light beam,and/or the wavelength of the light beam, and/or the amount of thereduced chromium catalyst, and/or the molar ratio of the reductant tochromium.

Aspect 38. A polymerization reactor system comprising:

the catalyst preparation system defined in any one of aspects 27-37; and

a reactor configured to contact the reduced chromium catalyst with anolefin monomer and an optional olefin comonomer under polymerizationreaction conditions to produce an olefin polymer.

Aspect 39. An olefin polymerization process comprising:

contacting the reduced chromium catalyst defined in aspect 26 and anoptional co-catalyst with an olefin monomer and an optional olefincomonomer in a polymerization reactor system under polymerizationreaction conditions to produce an olefin polymer.

Aspect 40. An olefin polymerization process comprising:

(I) irradiating a reductant and a supported chromium catalyst comprisingchromium in the hexavalent oxidation state with a light beam at awavelength in the UV-visible spectrum to reduce at least a portion ofthe supported chromium catalyst to form a reduced chromium catalyst; and

(II) contacting the reduced chromium catalyst and an optionalco-catalyst, with an olefin monomer and an optional olefin comonomer ina polymerization reactor system under polymerization reaction conditionsto produce an olefin polymer.

Aspect 41. The olefin polymerization process defined in aspect 39 or 40or the polymerization reactor system defined in aspect 38, wherein theolefin monomer comprises any olefin monomer disclosed herein, e.g., anyC₂-C₂₀ olefin.

Aspect 42. The olefin polymerization process defined in any one ofaspects 39-41 or the polymerization reactor system defined in aspect 38,wherein the olefin monomer comprises ethylene.

Aspect 43. The olefin polymerization process defined in any one ofaspects 39-42 or the polymerization reactor system defined in aspect 38,wherein the olefin monomer and the optional olefin comonomerindependently comprise a C₂-C₂₀ alpha-olefin.

Aspect 44. The olefin polymerization process defined in any one ofaspects 39-43 or the polymerization reactor system defined in aspect 38,wherein the catalyst is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Aspect 45. The olefin polymerization process defined in any one ofaspects 39-44 or the polymerization reactor system defined in aspect 38,wherein the catalyst is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 46. The olefin polymerization process defined in any one ofaspects 39-41 or the polymerization reactor system defined in aspect 38,wherein the olefin monomer comprises propylene.

Aspect 47. The olefin polymerization process defined in any one ofaspects 39-46 or the polymerization reactor system defined in aspect 38,wherein the polymerization reactor system comprises a batch reactor, aslurry reactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Aspect 48. The olefin polymerization process defined in any one ofaspects 39-47 or the polymerization reactor system defined in aspect 38,wherein the polymerization reactor system comprises a slurry reactor, agas-phase reactor, a solution reactor, or a combination thereof.

Aspect 49. The olefin polymerization process defined in any one ofaspects 39-48 or the polymerization reactor system defined in aspect 38,wherein the polymerization reactor system comprises a loop slurryreactor.

Aspect 50. The olefin polymerization process defined in any one ofaspects 39-49 or the polymerization reactor system defined in aspect 38,wherein the polymerization reactor system comprises a single reactor.

Aspect 51. The olefin polymerization process defined in any one ofaspects 39-49 or the polymerization reactor system defined in aspect 38,wherein the polymerization reactor system comprises two reactors.

Aspect 52. The olefin polymerization process defined in any one ofaspects 39-49 or the polymerization reactor system defined in aspect 38,wherein the polymerization reactor system comprises more than tworeactors.

Aspect 53. The olefin polymerization process defined in any one ofaspects 39-52 or the polymerization reactor system defined in aspect 38,wherein the olefin polymer comprises any olefin polymer disclosedherein.

Aspect 54. The olefin polymerization process defined in any one ofaspects 39-45 or 47-53 or the polymerization reactor system defined inaspect 38, wherein the olefin polymer comprises an ethylene/1-butenecopolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octenecopolymer.

Aspect 55. The olefin polymerization process defined in any one ofaspects 39-41 or 46-53 or the polymerization reactor system defined inaspect 38, wherein the olefin polymer comprises a polypropylenehomopolymer and/or a propylene-based copolymer.

Aspect 56. The olefin polymerization process defined in any one ofaspects 39-55 or the polymerization reactor system defined in aspect 38,wherein the polymerization conditions comprise a polymerization reactiontemperature in a range from about 60° C. to about 120° C. and apolymerization reaction pressure in a range from about 200 to about 1000psig (about 1.4 to about 6.9 MPa).

Aspect 57. The olefin polymerization process defined in any one ofaspects 39-56 or the polymerization reactor system defined in aspect 38,wherein the polymerization conditions are substantially constant, e.g.,for a particular polymer grade.

Aspect 58. The olefin polymerization process defined in any one ofaspects 39-57, wherein no hydrogen is added to the polymerizationreactor system.

Aspect 59. The olefin polymerization process defined in any one ofaspects 39-57, wherein hydrogen is added to the polymerization reactorsystem.

Aspect 60. The olefin polymerization process defined in any one ofaspects 39-59, wherein the wavelength comprises a single wavelength or arange of wavelengths in the visible spectrum (from 380 nm to 780 nm).

Aspect 61. The olefin polymerization process defined in any one ofaspects 39-59, wherein the wavelength comprises a single wavelength or arange of wavelengths in the 200 nm to 750 nm range.

Aspect 62. The olefin polymerization process defined in any one ofaspects 39-59, wherein the wavelength comprises a single wavelength or arange of wavelengths in the 300 to 750 nm range, the 350 nm to 650 nmrange, the 300 nm to 500 nm range, or the 300 nm to 400 nm range.

Aspect 63. The olefin polymerization process defined in any one ofaspects 39-59, wherein the wavelength comprises a single wavelength or arange of wavelengths below 600 nm, below 525 nm, or below 500 nm.

Aspect 64. The olefin polymerization process defined in any one ofaspects 39-63, wherein the wavelength is a single wavelength.

Aspect 65. The olefin polymerization process defined in any one ofaspects 39-63, wherein the wavelength is a range of wavelengths spanningat least 25 nm, at least 50 nm, at least 100 nm, at least 200 nm, etc.

Aspect 66. The olefin polymerization process defined in any one ofaspects 39-65, wherein the number-average molecular weight (Mn) of theolefin polymer is in any range disclosed herein, e.g., from about 5,000to about 150,000 g/mol, from about 5,000 to about 50,000 g/mol, fromabout 10,000 to about 100,000 g/mol, etc.

Aspect 67. The olefin polymerization process defined in any one ofaspects 39-66, wherein the weight-average molecular weight (Mw) of theolefin polymer is in any range disclosed herein, e.g., from about 50,000to about 700,000 g/mol, from about 75,000 to about 500,000 g/mol, fromabout 100,000 to about 400,000 g/mol, etc.

Aspect 68. The olefin polymerization process defined in any one ofaspects 39-67, wherein the density of the olefin polymer is in any rangedisclosed herein, e.g., from about 0.89 to about 0.96 g/cm³, from about0.91 to about 0.95 g/cm³, from about 0.91 to about 0.94 g/cm³, etc.

Aspect 69. The olefin polymerization process defined in any one ofaspects 39-68, wherein the melt index (MI) of the olefin polymer is inany range disclosed herein, e.g., from 0 to about 25 g/10 min, from 0 toabout 5 g/10 min, from 0 to about 1 g/10 min, etc.

Aspect 70. The olefin polymerization process defined in any one ofaspects 39-69, wherein the high load melt index (HLMI) of the olefinpolymer is in any range disclosed herein, e.g., from 0 to about 150 g/10min, from about 2 to about 120 g/10 min, from about 4 to about 50 g/10min, etc.

Aspect 71. The olefin polymerization process defined in any one ofaspects 39-70, wherein the MI (or HLMI) of the olefin polymer producedby the process is greater than 50% of, greater than 80% of, greater than100% of, greater than 120% of, greater than 150% of, etc., the MI (orHLMI) of an olefin polymer obtained using the supported chromiumcatalyst (without the irradiating step) and/or an olefin polymerobtained using an otherwise identical catalyst prepared using the samereductant at an elevated temperature (e.g., 300° C., 350° C., 400° C.,450° C., or 500° C.) without light irradiation, under the samepolymerization conditions.

Aspect 72. An olefin polymer produced by the olefin polymerizationprocess defined in any one of aspects 39-71.

Aspect 73. An article of manufacture comprising the olefin polymerdefined in aspect 72.

Aspect 74. The method, system or process defined in any one of aspects1-25 or 27-71, wherein the reductant comprises a compound with a C—Hbond or a H—H bond.

Aspect 75. The method, system or process defined in aspect 74, whereinthe reductant comprises a compound with a C—H bond.

Aspect 76. The method, system or process defined in aspect 74 or 75,wherein the reductant comprises a compound with a C—C bond.

Aspect 77. The method, system or process defined in aspect 74, whereinthe reductant comprises Hz.

Aspect 78. The method, system or process defined in aspect 74, whereinthe reductant comprises an alkane, an olefin, an aromatic, or anycombination thereof (e.g., a C₁ to C₃₆ alkane, olefin, and/or aromatic;a C₁ to C₁₈ alkane, olefin, and/or aromatic; a C₁ to C₁₂ alkane, olefin,and/or aromatic; or a C₁ to C₈ alkane, olefin, and/or aromatic);alternatively, the reductant comprises a linear, branched, or cyclicalkane compound having up to 18 carbon atoms; or alternatively, thereductant comprises a hydrocarbon aromatic compound having up to 18carbon atoms.

Aspect 79. The method, system or process defined in aspect 74, whereinthe reductant comprises ethylene, 1-butene, 1-hexene, 1-octene, methane,ethane, propane, isobutane, n-pentane, isopentane, n-hexane,tetrafluoroethane, cyclohexane, adamantane, decalin, benzene, toluene,etc., or any combination thereof.

Aspect 80. The method, system or process defined in any one of aspects1-25, 27-71, or 74-79, wherein a molar ratio of the reductant tochromium is in any suitable range or any range disclosed herein, e.g.,at least about 0.25:1, at least about 0.5:1, at least about 1:1, atleast about 10:1, at least about 100:1, at least about 1000:1, at leastabout 10,000:1, etc.

Aspect 81. An ethylene polymer having (or characterized by):

a ratio of Mw/Mn in a range from about 30 to about 110;

a ratio of Mz/Mw in a range from about 4 to about 10; and

a CY-a parameter in a range from about 0.2 to about 0.4.

Aspect 82. The polymer defined in aspect 81, wherein the ratio of Mw/Mnis in any range disclosed herein, e.g., from about 35 to about 105, fromabout 40 to about 100, from about 45 to about 95, or from about 50 toabout 90.

Aspect 83. The polymer defined in aspect 81 or 82, wherein the ratio ofMz/Mw is in any range disclosed herein, e.g., from about 5 to about 9,from about 5 to about 8, from about 5.5 to about 7.5, or from about 6 toabout 7.

Aspect 84. The polymer defined in any one of aspects 81-83, wherein theCY-a parameter is in any range disclosed herein, e.g., from about 0.23to about 0.38, from about 0.25 to about 0.35, or from about 0.27 toabout 0.34.

Aspect 85. The polymer defined in any one of aspects 81-84, wherein theethylene polymer has a Mn in any range disclosed herein, e.g., fromabout 3,000 to about 12,000 g/mol, from about 4,000 to about 11,000g/mol, from about 4,000 to about 10,000 g/mol, from about 5,000 to about10,000 g/mol, or from about 5,500 to about 9,500 g/mol.

Aspect 86. The polymer defined in any one of aspects 81-85, wherein theethylene polymer has a Mw in any range disclosed herein, e.g., fromabout 250,000 to about 700,000 g/mol, from about 300,000 to about675,000 g/mol, from about 350,000 to about 625,000 g/mol, or from about375,000 to about 600,000 g/mol.

Aspect 87. The polymer defined in any one of aspects 81-86, wherein theethylene polymer has a number of long chain branches (LCBs) in any rangedisclosed herein, e.g., from about 0.5 to about 4, from about 0.5 toabout 3, from about 0.7 to about 2.8, or from about 1 to about 2.5 LCBsper million total carbon atoms.

Aspect 88. The polymer defined in any one of aspects 81-87, wherein theethylene polymer has a HLMI in any range disclosed herein, e.g., lessthan or equal to about 10, less than or equal to about 8, less than orequal to about 5, or less than or equal to about 4 g/10 min.

Aspect 89. An ethylene polymer having (or characterized by):

a ratio of Mw/Mn in a range from about 6 to about 15;

a ratio of Mz/Mw in a range from about 30 to about 70; and

a melt index in a range from about 0.5 to about 10 g/10 min.

Aspect 90. The polymer defined in aspect 89, wherein the ratio of Mw/Mnis in any range disclosed herein, e.g., from about 7 to about 14, fromabout 8 to about 13, from about 8 to about 12, or from about 9 to about10.

Aspect 91. The polymer defined in aspect 89 or 90, wherein the ratio ofMz/Mw is in any range disclosed herein, e.g., from about 35 to about 65,from about 40 to about 60, from about 45 to about 55, or from about 47to about 51.

Aspect 92. The polymer defined in any one of aspects 89-91, wherein themelt index is in any range disclosed herein, e.g., from about 0.5 toabout 5, from about 0.7 to about 7, or from about 1 to about 5 g/10 min.

Aspect 93. The polymer defined in any one of aspects 89-92, wherein theethylene polymer has a Mn in any range disclosed herein, e.g., fromabout 10,000 to about 25,000 g/mol, from about 13,000 to about 22,000g/mol, from about 15,000 to about 20,000 g/mol, or from about 16,000 toabout 18,000 g/mol.

Aspect 94. The polymer defined in any one of aspects 89-93, wherein theethylene polymer has a Mw in any range disclosed herein, e.g., fromabout 100,000 to about 400,000 g/mol, from about 100,000 to about300,000 g/mol, from about 110,000 to about 250,000 g/mol, or from about140,000 to about 200,000 g/mol.

Aspect 95. The polymer defined in any one of aspects 89-94, wherein theethylene polymer has a number of long chain branches (LCBs) in any rangedisclosed herein, e.g., less than or equal to about 2, less than orequal to 1, less than or equal to about 0.8, less than or equal to about0.5, or less than or equal to about 0.2 LCBs per million total carbonatoms.

Aspect 96. An article of manufacture comprises the polymer defined inany one of aspects 81-95.

What is claimed is:
 1. A method for reducing a chromium catalyst forolefin polymerization, the method comprising: irradiating a reductantcomprising a C—H bond and a supported chromium catalyst comprisingchromium in the hexavalent oxidation state with a light beam at awavelength in the UV-visible spectrum to reduce at least a portion ofthe supported chromium catalyst to form a reduced chromium catalyst. 2.The method of claim 1, wherein: the reductant comprises ethylene,1-butene, 1-hexene, 1-octene, methane, ethane, propane, isobutane,n-pentane, isopentane, n-hexane, tetrafluoroethane, cyclohexane,adamantane, decalin, benzene, toluene, or any combination thereof; andthe supported chromium catalyst comprises a solid oxide selected fromsilica, alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania, zirconia,magnesia, boria, zinc oxide, silica-titania, silica-zirconia,alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria,silica-boria, aluminophosphate-silica, titania-zirconia, or anycombination thereof.
 3. The method of claim 1, wherein the supportedchromium catalyst comprises chromium/silica, chromium/silica-titania,chromium/silica-titania-magnesia, chromium/silica-alumina,chromium/silica-coated alumina, chromium/aluminophosphate, or anycombination thereof.
 4. The method of claim 1, wherein the supportedchromium catalyst has: a total pore volume in a range from about 0.9 toabout 3 mL/g; a BET surface area in a range from about 200 to about 700m²/g; and an average particle size in a range from about 25 to 250 μm.5. The method of claim 1, further comprising a step of calcining to formthe supported chromium catalyst comprising chromium in the hexavalentoxidation state.
 6. The method of claim 1, wherein: the reductantcomprises an alkane or aromatic hydrocarbon compound with up to 36carbon atoms; and the wavelength comprises a single wavelength or arange of wavelengths in a range from about 200 nm to about 750 nm. 7.The method of claim 1, wherein: the reductant comprises a compound witha C—C bond and a C—H bond; and the wavelength comprises a singlewavelength or a range of wavelengths below about 500 nm.
 8. The methodof claim 1, wherein: the light beam has an intensity of at least about500 lumens; the light beam has a power of at least about 50 watts; thereductant and the supported chromium catalyst are irradiated with anilluminance of at least about 2000 lux; or any combination thereof. 9.The method of claim 1, wherein: less than or equal to about 50 wt. % ofthe chromium in the reduced chromium catalyst is in the hexavalentoxidation state; and the chromium in the reduced chromium catalyst hasan average valence of less than or equal to about
 5. 10. The method ofclaim 1, wherein: the reduced chromium catalyst has a catalyst activityat least 10% greater than that of the supported chromium catalyst, underslurry polymerization conditions at a temperature of 105° C. and apressure of 550 psig; and/or the reduced chromium catalyst has acatalyst activity at least 10% greater than an otherwise identicalcatalyst prepared using the reductant at 400° C. without lightirradiation, under slurry polymerization conditions at a temperature of105° C. and a pressure of 550 psig.
 11. The reduced chromium catalystproduced by the method of claim
 1. 12. An olefin polymerization processcomprising: (I) irradiating a reductant comprising a C—H bond and asupported chromium catalyst comprising chromium in the hexavalentoxidation state with a light beam at a wavelength in the UV-visiblespectrum to convert at least a portion of the supported chromiumcatalyst to form a reduced chromium catalyst; and (II) contacting thereduced chromium catalyst and an optional co-catalyst with an olefinmonomer and an optional olefin comonomer in a polymerization reactorsystem under polymerization reaction conditions to produce an olefinpolymer.
 13. The process of claim 12, wherein: the reductant comprises ahydrocarbon compound with up to 36 carbon atoms; and the polymerizationreactor system comprises a loop slurry reactor, a fluidized bed reactor,a solution reactor, or a combination thereof.
 14. The process of claim12, wherein: the olefin polymer comprises an ethylene homopolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, anethylene/1-octene copolymer, a propylene homopolymer, a propylene-basedcopolymer, or a combination thereof; the HLMI of the olefin polymerproduced by the process is greater than 80% of that of (i) an olefinpolymer obtained using the supported chromium catalyst instead of thereduced chromium catalyst, and/or (ii) an olefin polymer obtained usingan otherwise identical reduced chromium catalyst prepared using thereductant at 400° C. without light irradiation, under the samepolymerization conditions.
 15. The process of claim 12, wherein: thereductant comprises a compound with a C—C bond; and a molar ratio of thereductant to chromium in the hexavalent oxidation state is at leastabout 1:1.
 16. A catalyst preparation system comprising: (a) a catalystpreparation vessel configured to irradiate a slurry of a supportedchromium catalyst in a diluent with a light beam at a wavelength in theUV-visible spectrum; (b) a catalyst inlet configured to introduce theslurry of the supported chromium catalyst into the catalyst preparationvessel, wherein at least a portion of the chromium is in the hexavalentoxidation state; and (c) a reduced catalyst outlet configured towithdraw a slurry of a reduced chromium catalyst from the catalystpreparation vessel.
 17. The catalyst preparation system of claim 16,further comprising (d) a controller configured to control a residencetime of the slurry of the supported chromium catalyst in the catalystpreparation vessel, a temperature of the catalyst preparation vessel, anintensity of the light beam, the wavelength of the light beam, an amountof the reduced chromium catalyst, a molar ratio of a reductant tochromium of the supported chromium catalyst, or any combination thereof.18. The catalyst preparation system of claim 16, wherein: a source ofthe light beam is sunlight, a fluorescent white light, a UV lamp, a LEDdiode, or any combination thereof; the wavelength comprises a singlewavelength or a range of wavelengths below 600 nm; the diluent comprisesa hydrocarbon; the system further comprises a lamp assembly inside oroutside the catalyst preparation vessel; and the system furthercomprises a co-catalyst inlet configured to introduce a co-catalyst feedstream into the catalyst preparation vessel.
 19. A polymerizationreactor system comprising: the catalyst preparation system of claim 16;and a reactor configured to contact the reduced chromium catalyst withan olefin monomer and an optional olefin comonomer under polymerizationreaction conditions to produce an olefin polymer, wherein the reactor isa loop slurry reactor, a fluidized bed reactor, a solution reactor, or acombination thereof.
 20. An ethylene polymer having: a ratio of Mw/Mn ina range from about 30 to about 110; a ratio of Mz/Mw in a range fromabout 4 to about 10; and a CY-a parameter in a range from about 0.2 toabout 0.4.
 21. An ethylene polymer having: a ratio of Mw/Mn in a rangefrom about 6 to about 15; a ratio of Mz/Mw in a range from about 30 toabout 70; and a melt index in a range from about 0.5 to about 10 g/10min.